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J^ 8910 



Bureau of Mines Information Circular/1982 




Thermodynamic Properties of Selected 
Transition Metal Sulfates 
and Their Hydrates 



By Carroll W. DeKock 




UNITED STATES DEPARTMENT OF THE INTERIOR 



Information Circular 8910 



Thermodynamic Properties of Selected 
Transition Metal Sulfates 
and Their Hydrates 



By Carroll W. DeKock 




UNITED STATES DEPARTMENT OF THE INTERIOR 
Jannes G. Watt, Secretary 

BUREAU OF MINES 
Robert C. Horton, Director 






This publication has been cataloged as follows: 





DeKock, Carroll W 




Thermodynamic properties of selected transition metal sulfates and 




their hydrates. 




(Information circular / United States Department of the Interior, 




Bureau of Mines ; 8910) 




Bibliography: p. 42-45. 




Supt. of Docs, no.: I 28.27:8910. 




1. Transition metal compounds— Thermal properties. 2. Sulphates- 




Thermal properties. 3. Hydrates— Thermal properties. I. Title. II. 




Series: Information circular (United States. Bureau of Mines) ; 8910. 




-^F^295tU4 [TN693.T7] 622s [549'. 75] 82-600258 



CONTENTS 

Page 

Abstract 1 

Introduction 1 

Methods , conventions , and symbols 1 

Estimation procedures for hydrates 3 

Discussion of thermodynamic properties 4 

Vanadium 4 

VOSOi+(c) 4 

V0S0i+-nH20(c) 4 

Chromium 4 

Cr2(S04)3(c) 4 

Cr2(SOi+)3«nH20(c) 4 

Manganese 5 

MnSOt+( c) 5 

MnS0^•H20(a,c) 5 

MnSOit«4H20(c) 5 

MnSOi+«5H20(c) 5 

MnSOit •7H20( c) 5 

Dissociation of MnS0i+»nH20(c) 6 

Iron 6 

FeSOit(c) and hydrates 6 

Fe2(S0O3(c) 7 

Cobalt 7 

CoSO^(c) 7 

CoS0i+«H20(c) 7 

CoS04»6H20(c) 7 

CoSOi+«7H20(c) 8 

Nickel 8 

NlS04(c) 8 

NlS0it»H20(c) 8 

NlS04»4H20(c) 8 

NlSOi+»6H20(c) 9 

NlSOi+»7H20(c) 9 

Copper 9 

CuSOt+Cc) 9 

CuS04'H20(c) and CuSOi+«3H20(c) 9 

CuSOi+ • 5H20( c) 9 

Cu2S04(c) 10 

CuO«CuSOit(c) 10 

Zinc 10 

ZnS04(c) 10 

ZnS0i+'H20(c) 11 

ZnS04»6H20(c) 11 

ZnS0i+«7H20(c) 11 

Zn0*2ZnS0i+(c) 11 

Thermal decomposition of anhydrous metal sulfates 11 

Tables 13 

References 42 



11 



ILLUSTRATIONS Page 

1. Gibbs energy of decomposition for Cr2(SOi+)3(c) and Fe2(S04)3(c) according to 

the reactions given in tables 53 and 55 12 

2. Gibbs energy of decomposition for FeSOi+(c) , CoSOi+Cc) , and NiSOi+Cc) according 

to the reactions given in tables 54, 56, and 57 12 

3. Gibbs energy of decomposition for CuSOi+(c) , CuO»CuSOi+(c) , ZnSOi+(c) , and 

ZnO*2ZnSOit(c) according to the reactions given in tables 58-61 12 

TABLES 

1. Thermodynamic properties of V0S04(c) 13 

2. Thermodynamic properties of V0S0i|»H20(c) 13 

3 . Thermodynamic properties of VOSOit •3H20( c) 14 

4. Thermodynamic properties of VOS04*5H20(a,c) 14 

5. Thermodynamic properties of VOSOt+«5H20(P,c) 15 

6. Thermodynamic properties of VOSOit»6H20(c) 15 

7. Thermodynamic properties of Cr2(SOi+)3(c) 

[Formation: 2Cr(c) + 3S(c,Jl) + 6 02(g) = Cr2(SO^)3(c) ] 16 

8. Thermodynamic properties of Cr2(SOi+)3(c) 

[Formation: 2Cr(c) + 1.5S2(g) + 6 02(g) = Cr2(SO^)3(c) ] 16 

9. Thermodynamic properties of [Cr2(H20)6(SOi+)3 ] •2H20(c) 17 

10. Thermodynamic properties of [Cr(H20)6] 2(SOi+)3 •2H20(c) 17 

11. Thermodynamic properties of [Cr(H20)6] 2(SOi+)3 •3H20(c) 18 

12. Thermodynamic properties of [Cr(H20)6] 2(80^)3 •4H20(c) 18 

13. Thermodynamic properties of [Cr(H20)6] 2(SOi+)3 •5H20(c) 19 

14. Thermodynamic properties of MnS0i4(c) 

[Formation: Mn(c) + S(c,Jl) + 2 02(g) = MnSOt+(c)] 19 

15. Thermodynamic properties of MnSOi+(c) 

[Formation: Mn(c) + 0.5S2(g) + 2 02(g) = MnSOi+(c)] 20 

16. Thermodynamic properties of MnS0it»H20(a,c) 20 

17. Thermodynamic properties of MnS0i+*4H20(c) 21 

18. Thermodynamic properties of MnSOi+*5H20(c) 21 

19. Thermodynamic properties of MnSOi+*7H20(c) 22 

20. Thermodynamic properties of FeSOt+(c) 

[Formation: Fe(c) + S(c,Jl) + 2 02(g) = FeSOit(c)] 22 

21. Thermodynamic properties of FeSOi+(c) 

[Formation: Fe(c) + 0.5S2(g) + 2 02(g) = FeS04(c)] 23 

22. Thermodynamic properties of FeS0i+»H20(c) 24 

23. Thermodynamic properties of FeS04»4H20(c) 24 

24. Thermodynamic properties of FeS0i4*7H20(c) 25 

25. Thermodynamic properties of Fe2(S04)3(c) 

[Formation: 2Fe(c) + 3S(c,l) + 6 02(g) = Fe2(SOi+)3(c) ] 25 

26. Thermodynamic properties of Fe2(SOtt)3(c) 

[Formation: 2Fe(c) + 1.5S2(g) + 6 02(g) = Fe2(S04)3(c) ] 26 

27. Thermodynamic properties of CoSOi+(c) 

[Formation: Co(c) + S(c,Jl) + 2 02(g) = CoSOit(c)] 26 

28. Thermodynamic properties of CoSOtt(c) 

[Formation: Co(c) + 0.5S2(g) + 2 02(g) = CoSOi+(c)] 27 

29. Thermodynamic properties of CoS0it*H20(c) 27 

30. Thermodynamic properties of CoSOit»6H20(c) 28 

31. Thermodynamic properties of CoSOi+*7H20(c) 28 

32. Thermodynamic properties of NiSOi+(c) 

[Formation: Ni(c) + S(c,i) + 2 02(g) = NiSO^(c)] 29 



iii 

TABLES — Continued Page 

33. Thermodynamic properties of NiSO^(c) 

[Formation: Ni(c) + 0.5 S2(g) + 2 02(g) = NiS04(c)] 29 

34. Thermodynamic properties of NiS0i+»H20(c) 30 

35. Thermodynamic properties of NiS0it»4H20(c) 30 

36. Thermodynamic properties of NiS0i|«6H20(a,c) 31 

37. Thermodynamic properties of NiS0i+»7H20(c) 31 

38. Thermodynamic properties of CuSOi+(c) 

[Formation: Cu(c) + S(c,Jl) + 2 02(g) = CuSOi+(c)] 32 

39. Thermodynamic properties of CuSO^(c) 

[Formation: Cu(c) + 0.5S2(g) + 2 02(g) = CuSOit(c)] 32 

40. Thermodynamic properties of CuS0i+»H20(c) 33 

41. Thermodynamic properties of CuS04»3H20(c) 33 

42. Thermodynamic properties of CuSOi+»5H20(c) 34 

43. Thermodynamic properties of Cu2S0i+(c) 34 

44. Thermodynamic properties of CuO»CuSOi^(c) 

[Formation: 2Cu(c) + S(c,Jl) + 2.5 02(g) = CuO«CuSOit(c) ] 35 

45. Thermodynamic properties of CuO»CuSOi+(c) 

[Formation: 2Cu(c) + 0.5S2(g) + 2.5 02(g) = CuO«CuSOi+(c) ] 35 

46. Thermodynamic properties of ZnSOit(c) 

[Formation: Zn(c,Jl) + S(c,Jl) + 2 02(g) = ZnSOit(c)] 36 

47. Thermodynamic properties of ZnS04(c) 

[Formation: Zn(c,Jl,g) + 0.5S2(g) + 2 02(g) = ZnSOi+(c)] 37 

48. Thermodynamic properties of ZnS0i+*H20(c) 37 

49. Thermodynamic properties of ZnS0i4»6H20(c) 38 

50 . Thermodynamic properties of ZnSOif • 7H20( c) 38 

51. Thermodynamic properties of ZnO«2ZnSOi+(c) 

[Formation: 3Zn(c,Jl) + 2S(c,Jl) + 4.5 02(g) = ZnO»2ZnSOt+(c)] 39 

52. Thermodynamic properties of ZnO*2ZnSOi+(c) 

[Formation: 3Zn(c,Jl,g) + S2(g) + 4.5 02(g) = ZnO»2ZnSOi+(c) ] 39 

53. Thermodynamic data for the reaction l/3Cr2(SOi+)3(c) = l/3Cr203(c) + S03(g).. 40 

54. Thermodynamic data for the reaction FeS04(c) = FeO(c) + S03(g) 40 

55. Thermodynamic data for the reaction l/3Fe2(SOit)3(c) = l/3Fe203(s) + S03(g).. 40 

56. Thermodynamic data for the reaction CoS0i+(c) = CoO(c) + S03(g) 40 

57. Thermodynamic data for the reaction NiS04(c) = NiO(c) + S03(g) 40 

58. Thermodynamic data for the reaction 2CuS0i+(c) = CuO«CuS04(c) + S03(g) 41 

59. Thermodynamic data for the reaction CuO•CuSO^(c) = 2CuO(c) + S03(g) 41 

60. Thermodynamic data for the reaction 3ZnS04(c) = ZnO»2ZnSOi+(c) + S03(g) 41 

61. Thermodynamic data for the reaction 0.5ZnO»2ZnSO4(c) = 1.5ZnO(c) + S03(g)... 41 



THERMODYNAMIC PROPERTIES OF SELECTED TRANSITION 
METAL SULFATES AND THEIR HYDRATES 

By Carroll W. DeKock ^ 



ABSTRACT 

Thermodynamic data for selected metal sulfates were critically evaluated and 
compiled as part of the Bureau of Mines program to provide a scientific base for use 
in developing new technology and predicting the feasibility of new processes. 
Values for Cp°, S°, H° - H298, -(G° - H298)/T, AHf°, AGf°, and log Kf as a function 
of temperature are given in tabular form. Thermodynamic data were compiled for 
VOSOi^, Cr2(S04)3, MnSOit, FeSOi^, Fe2(S04)3, CoSOit, NiSOi^, Cu2S04, CuSO^, CuO»CuSOi+, 
ZnSOit, and ZnO«2ZnSOi4, together with their stable hydrates. 

INTRODUCTION 

As a part of the Bureau of Mines continuing effort to provide thermodynamic 
data for mineral technology advancement, thermodynamic properties of selected tran- 
sition metal sulfates and their hydrates were critically evaluated and compiled. 
This compilation is the first in a planned series on the thermodynamic properties of 
metal sulfates. Kellogg (22), in 1964, reviewed the thermodynamic properties of 
many of the anhydrous metal sulfates found in this compilation. His values were 
based on high- temperature sulfate decomposition data. The thermodynamic properties 
here are calculated on the basis of calorimetric data, many of which were unavail- 
able in 1964. No review of the hydrated metal sulfates exists. 

This compilation has been prepared in the same format as Bureau of Mines Bul- 
letin 672, "Thermodynamic Properties of the Elements and Oxides," by L. B. Pankratz 
(36). The values for the standard heat capacities (Cp°), high-temperature relative 
enthalpies (H° - H598) , enthalpies of formation (AHf °) , and Gibbs energies of forma- 
tion (AGf°) are given in tabular form. The tables include Gibbs energy functions, 
-(G° - H298)/T, and logarithms (base 10) of the equilibrium constants of formation, 
log Kf. 

Where possible, all phases of an element or compound are presented in a single 
table. Temperatures of transformations and thermodynamic properties at these tem- 
peratures are included in the table. Immediately below the table, the nature of 
transformations are given along with their associated enthalpies. All thermodynamic 
values for the elements are from Pankratz (36). 

METHODS, CONVENTIONS, AND SYMBOLS 

The values in this compilation are the result of a review and critical evalua- 



Research chemist, Albany Research Center, Bureau of Mines, Albany, Oreg.; faculty 

!mber, Oregon Stat( 
2 
Underlined numbei 

end of this report. 



member, Oregon State University, Corvallis, Oreg. 
2 
Underlined numbers in parentheses refer to items in the list of references at the 



tion of relevant thermodynamic data through July 1981. Standard enthalpies of for- 
mation at 298.15 K are corrected to the latest CODATA (8^) values where the accuracy 
of the original djita warrants such care. The CODATA value for the standard heat of 
formation of S0^ (aq) at infinite dilution is the major correction for this docu- 
ment. CODATA gives AHf°(SO? , <=°aq) = -217.4 kcal/mol, while Wagman (47) reports 
AHf°(SO^ , "'aq) = -217.32 kcal/mol. Sulfate ion corrections in this document are 
all based on the CODATA value. Also, AHf°(H20,Jl) = -68.315 kcal/mol, used 
throughout this review, is from Wagman (47) . 

The selected experimental data were fitted to a polynomial in terms of tem- 
perature by using a modified form of the computer program described by Justice ( 20) . 
This program, along with a plot of the function (H° - H298)/(T-298.15) , which takes 
a known value of Cp° at 298.15 K, was used to merge high-temperature data smoothly 
with low-temperature heat capacity data. The resulting polynomial was then used in 
a subroutine of the program to calculate standard heat capacities, relative enthal- 
pies, Gibbs energy functions, and standard entropies at selected temperatures. In 
addition, tables 1-52 include values for the standard enthalpy of formation, Gibbs 
energy of formation, and the logarithm of the equilibrium constant of formation. 
Tabulated values are given for the substances in their standard states (indicated by 
the superscript "°"). 

References for data used in this compilation are given in the bibliography. 
Additional sources reviewed and considered less reliable are not included. Esti- 
mates are used where the necessary data were lacking, as explained in the section on 
estimation procedures. Estimated and extrapolated values are indicated in the 
source note below each table. 

The common practice of tabulating five- and sometimes six-digit values has been 
followed. For example, enthalpy values are given to the nearest calorie. The 
number of digits given is not intended to reflect the accuracy of the experimental 
values used, but rather to produce internal consistency in the tables. In the text, 
values are given to the significant figures to which they are thought to be accu- 
rate. 

The following is a list of symbols and constants used: 

T Thermodynamic temperature in kelvin. 
K Kelvin, the unit of thermodjmamic temperature. 
Cp Heat capacity at constant pressure. 
S Entropy. 
H - H298 Enthalpy increment between T and 298.15 K. 
(G - H298)/T Gibbs energy function, [(H - H298)/T] " S. 

AH Enthalpy change (AHf = enthalpy of formation). 
AG Gibbs energy change (AGf = Gibbs energy of forma- 
tion) . 
Log K Logarithm (base 10) of the equilibrium constant 
(Log Kf = logarithm of equilibrium constant of 
formation) . 
cal Thermochemical calorie, 1 cal = 4.1840 j. 
mol Mole, gram formula weight or molar mass. 
In Natural logarithm, base e = 2.7183. 
P Pressure in atmospheres, 1 atm = 101.325 kPa. 
R Gas constant, 1.98719 cal/mol«K. 
F Faraday constant, 23,060.9 cal/v»equiv. 
" Standard state. 



ESTIMATION PROCEDURES FOR HYDRATES 

The entropies and heat capacities for a number of hydrated sulfates in this 
study required estimation. Excellent heat capacity and entropy data are knovm for 
the 3d transition metal sulfate hydrates FeSOi+«7H20, CoSOi+«6H20, CoSOh«7H20, 
NiSOtt»6H20, NiSOit»7H20, CuS0it*H20, CuSOi+»3H20, CuSOt+»5H20, ZnSOit«6H20, and 
ZnSOi+»7H20. The average increase in heat capacity per water molecule for these 10 
compounds is 9.3 cal/mol»K. Phlllipson and Finlay (38), in a review of 31 hydrates, 
found a similar increase of 9.26 cal/mol»K per H2O molecule. Accordingly, the heat 
capacities for hydrates were estimated by adding 9.3 cal/mol"K per mole H2O to the 
heat capacity of the anhydrous compounds to obtain the heat capacity at 298.15 K. 
The entropy increase per mole of H2O for the 10 hydrates is 9.46 cal/mol*K. In the 
absence of other data for estimation, 9.5 cal/mol*K per mole H2O was added to the 
entropy of the anhydrous compound to obtain the entropy of the hydrate at 298.15 K. 
This was the only estimation method used for the vanadium and chromium sulfate 
hydrates. Other estimation procedures, tailored for individual compounds, are 
discussed in the text. 

With the values at 298.15 K in hand, it then was necessary to estimate the heat 
capacities above 298.15 K. This was a more complex problem because no data exist 
for any hydrates above about 350 K. For hydrates for which low-temperature data are 
available, heat capacities up to 550 K were estimated by extrapolating the low- 
temperature data, using a least squares fit with the quadratic equation, Cp = a + bT 
+ cT^. For salts for which data are not available, high-temperature heat capacities 
were estimated using the following equation: 

Cp(T) = Cp(298.15) + b(T-298.15), 

where b is a coefficient dependent on n, the number of water molecules. The values 
calculated for b are: 



1 


0.09 


2 


.10 


3 


.132 


4 


.144 


5 


.180 


6 


.216 


7 


.252 



These values of b were determined by observing that the heat capacity increase for 
tetrahydrates, hexahydrates, and heptahydrates averaged 1.8 cal/mol*K per mole H2O 
over the temperature range 250 to 300 K, a 50-degree interval. Similar data for 
dihydrates show an increase of 2.5 cal/mol*K, and for monohydrates, 4.5 cal/mol«K 
(14) . By linear interpolation, a value of 2.2 cal/mol»K was assigned for the tri- 
hydrates. 



DISCUSSION OF THERMODYNAMIC PROPERTIES 

Vanadium 

VOSOit(c) 

The enthalpy of formation at 298.15 K and entropy at 298.15 K are from Wagman 
(49). The heat capacity at 298.15 K was estimated to be 29 cal/mol*K by adding the 
heat capacity of VO (10.86 cal/mol*K) to the estimated heat capacity of the sulfate 
ion (18 cal/mol*K) (28) . High-temperature enthalpies were estimated by comparison 
with the known high-temperature enthalpies of MnSOit(c) (42). 

V0S0it»nH20(c) 

Reggiani, Tachez, and Bernard (41) determined the hydration enthalpies for the 
hydrated vanadyl sulfates, V0S0i+«nH20, by solution calorimetry. The standard 
enthalpies of formation of the hydrates at 298.15 K were determined from these data 
and the standard enthalpy of formation of VOSOi+(c) as reported by Wagman (49). The 
entropies at 298.15 K for the various hydrates were estimated by adding 9.5 cal/ 
mol»K per mole H2O to the entropy of VOSOi+(c). Heat capacities for the various 
hydrates were estimated as discussed earlier. 

Chromium 

Cr2(SOi,)3(c) 

Jacob, Rao, and Nelson (18) studied the decomposition of Cr2(SOt|)3 (c) over the 
temperature range 882 to 1,040 K, using thermogravimetric and differential thermal 
analyses. Over this temperature range, the change in the standard Gibbs energy for 
the reaction 

Cr203(c) + 3S03(g) = Cr2(S04)3(c) 

was found to be AG" = -143.078 + 0.1296T kcal/mol. This yielded a second-law value 
for AH° = -143.078 kcal/mol at 961 K for the above reaction. High-temperature 
enthalpies for Cr2(SOit)3(c) were estimated by adding the difference in known heat 
capacities between Cr2(S04)3(c) and Fe2(SOt|)3 (c) at 298.15 K (2.2 cal/mol«K) to the 
known high-temperature heat capacity of Fe2(SOi4)3 (c) (37) . This yielded an enthalpy 
difference between 298.15 K and 961 K equal to 61.4 kcal/mol. Combining this value 
with the appropriate enthalpies of Cr203(s) and S03(g) from Pankratz (36) yielded 
AHf°[Cr2(S04)3(c)] = -710 kcal/mol at 298.15 K. Alternatively, a third-law value 
may be obtained by combining the above heat capacity values with the low-temperature 
heat capacities measured by Vasileff and Grayson-Smith (45) to obtain the absolute 
entropy of Cr2(S04)3 in the temperature range of interest. The latter work yielded 
S298 = 61.85 cal/mol»K (28). This value and the heat capacities were used to obtain 
a third-law value of AHf'^Cr2(SOit)3 (c) ] = -705 kcal/mol, which is the adopted value. 

Cr2(S04)3 •nH20(c) 

Heat capacities and entropies for the chromium sulfate hydrates were estimated 
as discussed earlier for V0S0tt»nH20(c) . 



Manganese 
MnSOi+(c) 

The CODATA (8^) enthalpy of formation value for the sulfate ion at infinite 
dilution was used in recalculating the results of Southard and Shomate (42) to 
obtain AHf ° [MnSOi+(c) ] = -254.70 kcal/mol. This value is adopted. 

The enthalpy of solution at infinite dilution, AH°soln [MnSOit(c)] = -15.5 kcal/ 
mol^ is from Wagman (48) . When this value was combined with the CODATA value for 
SO^ (aq) and Wagman' s Mn^ (aq) value for the enthalpy of formation of the infinitely 
dilute ions, AHf ° [MnS04(c) ] = -254.66 kcal/mol was obtained, which is in excellent 
agreement with the adopted value. 

The entropy at 298.15 K is from Moore and Kelley (34) , who measured the low- 
temperature heat capacities of MnSOit(c). The high-temperature enthalpies are from 
Southard and Shomate (42) . 

MnS0i+«H20(a,c) 

The enthalpy of formation of MnS0i+«H20(a,c) is from Wagman (48) , corrected for 
the enthalpy of formation of the sulfate ion at infinite dilution. The entropy at 
298.15 K was estimated as follows: The average difference in entropy between the 
monohydrates and anhydrous salts for the sulfates of Fe , Ni , Cu, and Zn is 8.18 
cal/mol*K. Adding this value to the entropy of MnS0i+(c) yielded S298 = 35 cal/mol*K 
(rounded) . 

The heat capacity of MnS0it»H20(c) was estimated by adding 9.3 cal/mol«K to the 
heat capacity of MnSOi+(c) to give Cp298 = 33 cal/mol»K. 

MnSOit»4H20(c) 

The enthalpy of formation of MnSOit»4H20(c) at 298.15 K was taken from Wagman 
(48) after correcting for the enthalpy of formation of the sulfate ion (8^). The 
heat capacity at 298.15 K was estimated by adding 4*9.3 cal/mol»K to the heat 
capacity of MnSOi+(c) . The entropy at 298.15 K was estimated to be 65 cal/mol*K as 
discussed under "MnSOi+»7H20." 

MnSOi+«5H20(c) 

The enthalpy of formation of MnS0i+*5H20(c) at 298.15 K was taken from Wagman 
(48) after correcting for the enthalpy of formation of the sulfate ion (8^). The 
heat capacity at 298.15 K is from Wagman. The entropy was estimated to be 75 
cal/mol»K as discussed under "MnSOi+*7H20." 

MnS0i+«7H20(c) 

The enthalpy of formation of MnS0i+»7H20(c) at 298.15 K was taken from Wagman 
( 48 ) after correcting for the enthalpy of formation of the sulfate ion (8). The 
entropy at 298.15 K was estimated as follows. The entropies of the heptahydrates of 
the sulfates of Fe, Co, Ni, and Zn are well known (4, 30, 40, 43) . The average 
difference between the entropies of these heptahydrates and their anhydrous sulfates 
is 67.65 ±1.25 cal/mol»K. Adding this value to the entropy of MnS0i+(s) at 298.15 K 
yielded S298[MnS0it •7H20(c) ] = 94 cal/mol«K (rounded). The entropies for MnSOi+« 



4H20(c) and MnSOi+*5H20(c) were then estimated by taking the difference for the 
monohydrate and heptahydrate (59 cal/mol*K) and adding the linear extrapolated 
entropy proportion to the entropy of the monohydrate to obtain the entropy of the 
tetra- and pentahydrate. 

The heat capacity of MnSOit»7H20(c) was estimated in the same manner as the en- 
tropy. 

Dissociation of MnS0it»nH20 

Thermodynamic values for reactions of the type 

MnS04»YH20(c) = MnS04«XH20(c) + (Y-X)H20(Jl) 

were calculated as a function of temperature. The foregoing data gave reasonable 
decomposition temperatures for all the compounds. However, enthalpy of formation 
values for the hydrates that were calculated on the basis of either the enthalpy of 
solution values reported by Jamieson (19) or those reported by Phillipson and Finlay 
( 38 ) led to inconsistent results and were not sufficiently negative to lead to 
stable hydrates. 

Iron 

FeSOit(c) and Hydrates 

Adami and Kelley (1) determined the enthalpy of formation of FeS0t+*H20(c) and 
FeSOit*7H20(c) by sulfuric acid solution calorimetry. Recalculation of their results 
using the latest CODATA (8) value for SO^ (aq) yielded AHf ° [FeS04«H20(c)] = -297.40 
kcal/mol and AHf ° [FeS04*7H20(c)] = -720.44 kcal/mol. These values are adopted. 
Wagman (48^) reported AHf ° [FeS0it»H20(c) ] = -297.25 kcal/mol and AHf ° [FeSO^•7H20(c) ] = 
-720.5 kcal/mol. The enthalpies of solution at infinite dilution, AH°soln[FeSOt+« 
H20(c)] = -10.6 kcal/mol and AH°soln[FeS0i+»7H20(c) ] = 2._p2 kcal/mol, have been 
measured by Larson (29) . The enthalpy of formation for Fe^ (aq) may be obtained by 
combining these values with AHf° values for H20(A) ( 47 ) and SO^ (aq) (8^). This 
leads to AHf°[Fe2 (aq)] = -22.3 kcal/mol(FeS0it«H20) and AHf°[Fe2 (^^^j = -22.0 
kcal/mol(FeS04*7H20) , respectively. These are more negative than the value given by 
Wagman (48), AHf°[Fe2 {^'^^^ "^ -21.3 kcal/mol. Larson ( 29 ) noted a similar discrep- 
ancy and chose AHf°[Fe (aq) ] = -22.1 kcal/mol. We have adopted his value in our 
further calculations. 

Combining the enthalpy of solution at infinite dilution from Wagman (48) , 
AH°soln [FeSOit(c)] = +16.7 kcal/mol, with the above enthalpy of formation "Tor 
Fe^ (aq) and the enthalpy of formation for SO^ (aq) from CODATA (8^) yielded 
AHf °[FeS0^(c)] = -222.8 kcal/mol, which is the value adopted here. This compares 
with AHf°[FeS0it(c)] = -221.9 kcal/mol given by Wagman (48). 

Combining the enthalpy of solution at infinite dilution, _AH°soln[FeS0t+»4H20(c) ] 
= -3.3 kcal/mol (29) , with the enthalpies of formation of S0$ (aq) (8^), H20(J!,) (47) , 
and Fe2 (aq) yielded AHf ° [FeSOit •4H20(c) ] = -509.5 kcal/mol, which is the adopted 
value. This compares with AHf ° f FeS0H»4H20(c) ] = -508.9 kcal/mol reported by Wagman 
(48). 

Malinin, Drakin, and Ankudimov (32) measured the entropy of the reaction 
FeS04«7H20(c) = FeS0^•4H20(c) + 3H20(g)~by an isopiestic method. Their value for 



this reaction was AS = 105.0 cal/mol'K. Combining this value with the entropies of 
FeSOit«7H20(c) (30) and H20(g) (47^) led to S598[FeS04«4H20(c) ] = 67.5 cal/mol»K. 
S298 for FeS0^•H20(c) is from Pribylov (39) . The heat capacity for FeS0it»H20(c) was 
estimated as discussed earlier. The heat capacity for FeS0i+«4H20(c) was reported by 
Kelley (21) to be 63.6 cal/mol»K at 282 K. 

The heat capacity above 307 K for FeS0it»7H20(c) was estimated by extrapolating 
the low- temperature results of Lyon and Giauque (30). 

Fe2(S0^)3(c) 

Barany and Adami (3) determined the enthalpy of formation of Fe2( 804) 3(c) by 
solution calorimetry. Recalculation_ of their results using the latest CODATA value 
for the enthalpy of formation of S04 (aq) (8) and Wagman's enthalpy of formation for 
Fe203(c) (48) yielded AHf ° [Fe2(S04)3 ] = -617.1 kcal/mol, which is adopted here. 

The low-temperature and high-temperature heat capacities are those reported by 
Pankratz and Weller (37) . The entropy at 298.15 K is also taken from reference 37. 

Cobalt 

CoS0^(c) 

The CODATA AH° value (8^) for SO^ (aq) and the heat of formation value recom- 
mended by Cyr, Dellacherie, and Balesdent (9) for CoO were used in recalculating the 
results of Adami and King {1) to obtain AHf ° [CoS0i+(c) ] = -212.3 kcal/mol. This 
value is adopted here. 

The low-temperature (52-298.15 K) heat capacities are those reported by Weller 
(50) with the low-temperature entropies and enthalpies those evaluated by JANAF 
(11) . Heat capacities in the temperature range 300-1,400 K were estimated by com- 
parison with CuSOi+(c). 

The transition temperature and enthalpy for CoSOi+(a,c) = CoSOi|(P,c) are from 
the differential thermal analysis studies of Ingraham and Marier (17). 

CoS0h»H20(c) 

Goldberg ( 15) reported AH° = -6.1 kcal/mol for the process CoSO^(c) + H20(A) = 
CoS0i^»H20(c) . Combining this result with the standard enthalpies of formation of 
H20(Jl) and CoS04(c) yielded AHf ° [CoS0i+-H20(c)] = -286.7 kcal/mol. Alternatively, 
Goldberg reported AH° = -12.8 kcal/mol for the process CoS0^•H20(c) + 5H20(J!.) = 
CoS0it«6H20(c) . Combining this result with the standard enthalpies of formation of 
H20(Jl) (47^) and CoS0i4«6H20(c) (see below) yielded AHf ° [CoS04«H20(c) ] = -287.0 
kcal/mol. The average of these two values, AHf ° [CoS0it*H20(c) ] = -286.8 kcal/mol, is 
adopted. The entropy at 298.15 K is that selected by Goldberg (15) . Heat capaci- 
ties were estimated as described earlier. 

CoS0i+'6H20(c) 

Ko and Brown (25) , from sulfuric acid solution calorimetry, obtained 
AHf° [CoS04»6H20(c) ] = -641.33 kcal/mol, which is adopted here. The low-temperature 
(15-330 K) heat capacities and S298 ^^e those reported by Rao and Giauque (40) . 
Broers and Van Welie (6) reported CoS0i+«6H20(c) to dissociate to CoS0^•H20(c) and 



saturated solution at 337 K. 

CoSO^•7H20(c) 

Brodale and Giauque (_5) reported AH° = -2.455 kcal/mol for the process CoSOi+» 
6H20(c) + H20(J!.) = CoSOi4»7H20(c) . Combining this value with the standard enthalpies 
of formation of H20(Jl) and CoS04«6H20(c) yielded AHf ° [CoSOit»7H20(c)] = -712.10 kcal/ 
mol, which is the adopted value. The low-temperature (15-310 K) heat capacities and 
S298 are those reported by Rao and Giauque (40) . They found that the transition 
CoS0i4»7H20(c) to CoSOit»6H20(c) and saturated solution occurs at 317.78 K with an 
enthalpy of transition equal to 2.848 kcal/mol heptahydrate. 

Nickel 

NiSOit(c) 

The CODATA AHf ° [SO^~(aq) ] value (8^) was used in recalculating the results of 
Adami and King (2^) to obtain AHf ° [NiSO^(c) ] = -208.71 kcal/mol. This value is 
adopted. Low- temperature (9-70 K) heat capacities of NiS0i4(c) were measured by 
Stuve, Ferrante, and Ko ( 44) and have been combined with earlier work of Weller ( 50 ) 
to provide data to 300 K. It is noted that Cp298[NiSOit(c) ] = 33 cal/mol*K, reported 
by Wagman (48), is in error. The correct value is 23.33 cal/mol"K, as reported by 
Weller (50) . High-temperature enthalpy data (to 1,200 K) for NiS04(c) are taken 
from the work of Stuve, Ferrante, and Ko. 

NiS0i+»H20(c) 

The enthalpy of solution at infinite dilution, AH°soln[NiS0i+«H20(c)] = -14.0 
kcal/mol, is taken from the work of Goldberg (15) . Combining this result with the 
CODATA value for SO^ (aq) (8^) and Wagman' s value for Ni^ (aq) (48) for the enthalpy 
of formation of the infinitely dilute ions, yielded AHf " [NlS0i+»H20(c) ] = -284.61 
kcal/mol. S298 estimated by Mah and Pankratz (31) is adopted, and the heat capaci- 
ties were estimated as discussed in the section "Estimation Procedures for 
Hydrates." 

NiS0H»4H20(c) 

Kohler and Zaske (26) reported the vapor pressure as a function of temperature 
over the range 313-326 k7 for the reaction NiSOt+«6H20(c) = NiS0^•4H20(c) + 2H20(g) . 
Their data gave AG298 = +5.053 kcal for this reaction. The entropy of NiS0^•4H20(c) 
was estimated by noting that S|98 [NiSOij •6H20(c) ] = 79.94 cal/mol»K, while 
S298[NiS0it(c)] = 24.2 cal/mol»K. Linear interpolation yielded S°298[NiS0if«4H20(c) ] 
= 61 cal/mol»K. Combining the above value with the standard Gibbs energy change for 
H20(g) to H20(Ji) (47) yielded AH = -5.3 kcal for the reaction NiS0i4»4H20(c) + 
2H20(Jl) = NiS0i+»6H20rc) . This value combined with the standard enthalpy of forma- 
tion of NiSOi+«6H20 (see below) and H20(A) (47) yielded AHf ° [NiS0i4«4H20(c)] = -499.4 
kcal/mol, which is the adopted value. Wagman ( 48 ) reported AHf °[NiS0tt»4H20(c) ] = 
-502.9 kcal/mol. However, using the latter value with the above estimated entropy 
requires NiS04«6H20(c) to be unstable with respect to NiS0^•4H20(c) and 2H20(J?,) at 
298 K. Alternatively, accepting Wagman' s value for the enthalpy of formation of 
NiS0i4»4H20(c) (48) together with the above Gibbs energy data of Kohler and Zaske 
( 26) requires S298[NiS04»4H20(c)] = 53 cal/mol»K. This value is too low to be 
acceptable. Using the above adopted value AHf ° [NiS0it«4H20(c) ] = -499.4 kcal/mol, 
NiS0i4*6H20(c) was calculated to be stable to 360 K with respect to NiS0i+»4H20(c) and 



2H20(J!.). Cp°(NiS04*4H20) and its temperature dependence were estimated as described 
earlier. 

NiSOit«6H20(c) 

Goldberg (15) reported the enthalpy of solution at infinite dilution, AH°soln 
[NiSOi+«6H20(c)]'~^ +1.15 kcal/mol. Combining this result with CODATA (8) values for 
the heat of formation of SO^ (aq) ion at infinite dilution and AHf(H20,Jl) together 
with AHf°[Ni2"^(aq)] (48) yielded AHf " [NiS04»6H20(c) ] = -641.34 kcal/mol, which is 
the adopted value. Low-temperature (1.1-320.98 K) heat capacities and entropies are 
those reported by Stout (43) . 

NiSO^«7H20(c) 

Goldberg (15) reported the enthalpy of solution at infinite dilution, AH°soln 
[NiS04»7H20(c)]'~= +2.89 kcal/mol. Combining this value with the enthalpies of 
formation of Ni^ (aq) and SO^ (aq) at infinite dilution together with the standard 
enthalpy of formation of water yielded AHf ° [NiSOi+»7H20(c) ] = -711.40 kcal/mol, which 
is the adopted value. Low-temperature (1-300 K) heat capacities and entropies are 
those reported by Stout (43). Stout ( 43 ) reported the transition from NiS0i+«7H20(c) 
to NiS0i+«6H20(c) , and saturated solution occurs at 304 K. Additional differential 
scanning calorimeter (DSC) data for the above nickel sulfate hydrates were given by 
Friesen, Burt, and Mitchell (13). 

Copper 

CuS04(c) 

The CODATA (8^) values for the standard enthalpy of formation and entropy at 298 
K for CuSOij(c) are adopted. The heat capacities are those adopted by King, Mah, and 
Pankratz (23) . The enthalpy of solution at infinite dilution, AH°soln[CuS0i+(c) ] = 
-17.56 kcal/mol was reported by Larson (29) . Combining this result with the CODATA 
values for the enthalpies of formation of the infinitely dilute ions yielded 
AHf°[CuSO^(c)] = -184.14 kcal/mol, which is to be compared with the adopted CODATA 
value of -184.3 kcal/mol. 

CuS04«H20(c) and CuS04»3H20(c) 

The standard enthalpies of formation, entropies, and heat capacities at 298.15 
K are those from Wagman (48). The high-temperature heat capacities were estimated. 

CuSOi+«5H20(c) 

The heat of solution at infinite dilution, AH''soln[CuSOi+»5H20(c) ] = +1.43 
kcal/mol, was reported by Larson (29). Combining this result with the heat of solu- 
tion of CuSO^ (see above) yielded AH° = +18.99 kcal/mol for the reaction CuSO^• 
5H20(c) = CuS04(c) + 5H20(Jl). Combining this result with the CODATA (8) values for 
the standard enthalpies of formation of CuS04(c) and H20(A) yielded AHf°[CuS04« 
5H20(c)] = -544.87 kcal/mol, which is the adopted value. Alternatively, combining 
the enthalpies of formation of the ions at infinite dilution with the enthalpy of 
formation of water and the enthalpy of solution at infinite dilution of CuSOi+» 
5H20(c) gave AHf ° [CuSOit«5H20(c) ] = -544.71 kcal/mol, in good agreement with the 
adopted value. The entropy and heat capacity values at 298.15 K are those reported 
by Wagman (48). The high-temperature heat capacities were estimated. 



10 

Malinin, Drakln, and Ankudimov (33), from vapor pressure measurements of water 
over CuSOi+»5H20(c) at 24.06 and 31.47'^, calculated AG° = 5.4 kcal, AS° = 72 cal/K, 
and AH° = 27 kcal at 298.15 K for the reaction 

CuSOi+-5H20(c) = CuSOit«3H20(c) + 2H20(g) . 

This Is in good agreement with the data given here, for which AG° = 5.46 kcal, AS° = 
71.3 cal/mol«K, and AH° = 26.7 kcal at 298.15 K. 

Cu2S0t+(c) 

The enthalpy of formation at 298.15 K is from Wagman (48) . The entropy at 
298.15 K was estimated by Nagamori and Habashi (35) , using Latimer's method. The 
heat capacities were estimated by comparison with K2S0it(c) (10). 

CuO«CuSOi+(c) 

All data for CuO»CuSOit(c) are from the compilation of King, Mah, and Pankratz 
(23). 

Zinc 

ZnS04(c) 

CODATA (8^) enthalpy of formation values for SO^ (aq) and ZnO(c) were used in 
recalculating the results of Adami and King (2) to obtain AHf °[ZnSOi+(c)] = -234.26 
kcal/mol. JANAF (j^) reported the same value for ZnS04(c) . This value is adopted 
here. The enthalpy of solution at infinite dilution, AH''soln[ZnSOit(c) ] = -19.9 
kcal/mol, was taken from Larson (29). Combining this result with the CODATA values 
for the heats of formation of the" infinitely dilute ions yielded AHf ° [ZnS04(c) ] = 
-234.16 kcal/mol. 

Low-temperature heat capacities of ZnSOit(a,c) have been measured by Weller ( 50 ) 

from 51.7 to 296.5 K. We adopt his entropy and heat capacity values in this region. 

High-temperature enthalpy data have been measured by Hosmer and Krikorian (16) as 

well as by Voskresenskaya and Patsukova (46) and Krestovnikov and Feigina ( 27 ) . The 

enthalpy data of Hosmer and Krikorian (16) lie above those of 46 and 27. Hosmer and 

Krikorian reported that the low values of 46 and 27 may be due to decomposition to 

the oxysulfate during vacuum dehydration. Chemical analysis of the sample of Hosmer 

and Krikorian indicated pure ZnSOit(c) . However, serious problems remain in matching 

the low- temperature heat capacity data with the high-temperature enthalpy data of 

Hosmer and Krikorian. JANAF ( 12) recognized this problem and arbitrarily assigned a 

transition at 540 K with AH° = 1.20 kcal/mol. There is no evidence in the litera- 

tr 
ture for such a transition and Brown (7) found none by DSC measurements in our 

laboratories. In addition, the data of" Voskresenskaya and Patsukova (46) match 
nicely the low-temperature heat capacity data of Weller (50). Therefore, the high- 
temperature enthalpy data of 46 for ZnS04(a,c) are adopted. 

The transition of ZnS0i+(a,c) to ZnS04(P,c) occurs at 1,015 ±15 K with a AH° 
given by Hosmer and Krikorian (16) as 4.87 kcal/mol, which is the adopted value. 
This value is in good agreement with that reported by Ingraham and Marier (jLT^, 4.74 
kcal/mol) from differential thermogravimetric analysis (DTA) measurements. 



11 



ZnS0i+»H20(c) 

The enthalpy of solution at infinite dilution was calculated from Wagman (47) 
to be AH°soln [ZnS0^•H20(c)] = -10.63 kcal/mol. Combining this result with the heat 
of solution of ZnSOit(c) (27) and the heat of formation of ZnSOi+(c) and H20(A) (47) 
yielded AHf °[ZnS0i+»H20(c)] = -311.85 kcal/mol, which is the adopted value. 

The entropy at 298.15 K is taken from Wagman (47), and the heat capacity at 282 
K was reported by Kelley ( 21) to be 34.7 cal/mol«K. The high-temperature heat 
capacities were extrapolated as discussed earlier. 

ZnSO^•6H20(c) 

The enthalpy of solution at infinite dilution, AH°soln[ZnSOi+»6H20(c) ] = -0.15 
kcal/mol was reported by Larson (29) . Combining this value with the enthalpy of 
solution of ZnSOtt(c) (29) and the adopted enthalpy of formation of ZnSOit(c) and 
Wagman's H20(Jl) (47) yielded AHf °[ZnSOi+»6H20(c)] = -663.90 kcal/mol, which is the 
adopted value. The entropy and heat capacity at 298.15 K are taken from Barieau and 
Giauque (4). They also reported that ZnSOi4»6H20(c) decomposes to the monohydrate 
and saturated solution at 60.3° C. Heat capacities above 310 K, the highest temper- 
ature reported by Barieau and Giauque, were extrapolated by fitting the lower 
temperature data as discussed earlier. 

ZnS0it»7H20(c) 

The enthalpy of solution at infinite dilution, AH°soln[ZnSOit»7H20(c)] = 3.18 
kcal/mol, was reported by Larson (29) . Combining this value with the heat of solu- 
tion of ZnS04(c) (29) and the enthalpies of formation of ZnS0i+(c) and H20(A) (47) 
gave AHf °[ZnS0i+»7H20(c)] = -735.55 kcal/mol. The entropy and heat capacities are 
from Barieau and Giauque (4), who reported that the transition of ZnS04«7H20(c) to 
ZnS04»6H20(c) and H20(Jl) oc"curs at 311.27 K with AH° = 4.017 kcal/mol. 

Zn0«2ZnS0it(c) 

Ko and Brown (25), from hydrochloric acid solution calorimetry, determined 
AHf°[Zn0»2ZnS0i+(c)] = -550.31, which is the adopted value. High-temperature 
enthalpy data for Zn0»2ZnS0it(c) were reported by Hosmer and Krikorian (16) . Their 
$298 = 68.19 cal/mol*K and high-temperature enthalpy values are adopted. 

THERMAL DECOMPOSITION OF ANHYDROUS METAL SULFATES 

The thermodynamic properties for the thermal decomposition of anhydrous metal 
sulfates were calculated as a function of temperature. These data are given in the 
auxiliary tables 53-61 and are plotted in figures 1-3. These tables and figures 
enable the reader to make a ready comparison of the stabilities of these metal 
sulfates as a function of temperature. For CuSOi^(c) and ZnSOi+(c), the decomposition 
proceeds through the oxysulfates (22). The decomposition equations are: 

2CuS0it(c) = CuO«CuSOi+(c) + S03(g); 

Cu0»CuS0i+(c) = 2Cu0(c) + S03(g); 

3ZnS0it(c) = ZnO•2ZnSO^(c) + S03(g); 



12 



ZnO«2ZnSOi+(c) = 3ZnO(c) + 2S03(g). 

The remaining systems all decompose directly to the metal oxide and S03(g) (22) . 
Recall that the equilibrium, 

S02(g) + 0.5 02(g) = S03(g), 

becomes important at higher temperatures. That the S02(g)-S03(g) equilibrium is 
attained is critical for the evaluation of the experimental decomposition data. 
However, recent work (24) indicates that attainment of equilibriiim depends on the 
solids involved and whether or not a catalyst is present. 



32 



KEY 

Cr2(S04)3 

Fe2(S04)3 




500 600 700 800 

TEMPERATURE, K 



900 



FIGURE To - Gibbsenergy of decomposition for 
CrjCSO 4)3(0) and Fe2(S04)3(c) according to the 
reactions given in tables 53 and 55. 



o 

o 



< 



1 1 <— 

KEY 

FeS04 

C0SO4 

NiS04 





800 



900 1,000 1,100 

TEMPERATURE, K 



1,200 



FIGURE 2o = Gibbsenergy of decomposition for 
FeS04(c), CoS04(c), and NiS04(c) according to 
the reactions given in tables 54, 56, and 57., 



24 



"T 1 T- 



KEY 

CUSO4 

CuO-CuS04 - 

Z nS04 

ZnO-2ZnS04 




800 900 1,000 1,100 

TEMPERATURE, K 



1,200 



FIGURE 3. ° Gibbs energy of decomposition for 
CuSO^(c), CuO-CuSO^(c), ZnS04(c), and ZnO 
2ZnS0 .(c) according to the reactions given in 
tables 58-61. 



13 



TABLE 1. - Thermodynamic properties of VOSOi,(c) 
[Formation: V(c) + S(c,i) + 2.5 OjCg) = VOSO^(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- H2,a)/T 


LjO ijO 

H - Hjse 


AHf 


AGf 


298.15 


29.000 


26.000 


26.000 





-312.900 


-279.779 


205.081 


300 


29.066 


26.180 


26.000 


.054 


-312.900 


-279.573 


203.666 


368.30 


31.305 


32.373 


26.619 


2.119 


-312.841 


-271.990 


161.397 


368.30 


31.305 


32.373 


26.619 


2.119 


-312.937 


-271.990 


161.397 


388.36 


31.962 


34.051 


26.961 


2.754 


-312.905 


-269.760 


151.806 


388.36 


31.962 


34.051 


26.961 


2.754 


-313.318 


-269.760 


151.806 


400 


32.344 


35.001 


27.181 


3.128 


-313.314 


-268.455 


146.675 


432.02 


33.250 


37.527 


27.855 


4.178 


-313.307 


-264.865 


133.988 


500 


35.174 


42.531 


29.515 


6.508 


-313.334 


-257.234 


112.436 


600 


37.555 


49.161 


32.248 


10.148 


-313.088 


-246.032 


89.616 


700 


39.487 


55.101 


35.095 


14.004 


-312.642 


-234.890 


73.335 


717.82 


39.751 


56.097 


35.604 


14.710 


-312.544 


-232.911 


70.912 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° r kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 



Sources: The enthalpy of formation at 298 K and entropy at 298 K are from Wagman (49). 
heat capacities are estimates. 



The 



TABLE 2. - Thermodynamic properties of V0S0h*H20(c) 
[Formation: V(c) + S(c,il) + 3 OzCg) + HjCg) = VOSO^'HjOCc)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(C- H|98)/T 


IjO IjO 

H - Hjse 


AHf° 


AGf 


298.15 


38.000 


35.500 


35.500 





-387.550 


-340.652 


249.701 


300 


38.167 


35.736 


35.503 


.070 


-387.553 


-340.361 


247.949 


350 


42.667 


41.957 


35.983 


2.091 


-387.518 


-332.496 


207.617 


368.30 


44.314 


44.173 


36.335 


2.887 


-387.458 


-329.620 


195.595 


368.30 


44.314 


44.173 


36.335 


2.887 


-387.554 


-329.620 


195.595 


388.36 


46.119 


46.571 


36.801 


3.794 


-387.460 


-326.466 


183.717 


388.36 


46.119 


46.571 


36.801 


3.794 


-387.873 


-326.466 


183.717 


400 


47.167 


47.948 


37.106 


4.337 


-387.823 


-324.627 


177.365 


432.02 


50.049 


51.689 


38.047 


5.894 


-387.649 


-319.574 


161.664 


450 


51.667 


53.763 


38.634 


6.808 


-387.590 


-316.742 


153.829 


500 


56.167 


59.440 


40.432 


9.504 


-387.121 


-308.893 


135.015 


550 


60.667 


65.004 


42.413 


12.425 


-386.432 


-301.100 


119.644 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



Sources: The enthalpy of formation at 298 K is based on Reggiani (41), 
entropy at 298 K and the heat capacities are estimates. 



The 



14 



TABLE 3. - Thermodynamic properties of V0S0h*3H20(c) 
[Formation: V(c) + S(c,A) + 4 OjCg) + 3H2(g) = V0S0h*3H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp- 


S" 


-(G°- H|9a)/T 


H°- H|,8 


AHf 


AGf° 


298.15 


57.000 


54.500 


54.500 





-533.880 


-459.427 


336.765 


300 


57.244 


54.853 


54.500 


.106 


-533.886 


-458.964 


334.351 


350 


63.844 


64.173 


55.222 


3.133 


-533.890 


-446.473 


278.787 


368.30 


66.260 


67.488 


55.749 


4.323 


-533.819 


-441.904 


262.223 


368.30 


66.260 


67.488 


55.749 


4.323 


-533.915 


-441.904 


262.223 


388.36 


68.908 


71.071 


56.448 


5.679 


-533.796 


-436.895 


245.860 


388.36 


68.908 


71.071 


56.448 


5.679 


-534.209 


-436.895 


245.860 


400 


70.444 


73.129 


56.904 


6.490 


-534.137 


-433.979 


237.112 


432.02 


74.671 


78.714 


58.314 


8.813 


-533.875 


-425.972 


215.487 


450 


77.044 


81.807 


59.191 


10.177 


-533.750 


-421.484 


204.698 


500 


83.644 


90.266 


61.876 


14.195 


-533.026 


-409.044 


178.791 


550 


90.244 


98.548 


64.835 


18.542 


-531.985 


-396.693 


157.629 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol 



0.096 kcal/mol. 



Sources: The enthalpy of formation at 298 K is based on Reggiani (41 ). 
entropy at 298 K and the heat capacities are estimates. 



The 



TABLE 4. - Thermodynamic properties of V0S0^*5H20(a,c) 
[Formation: V(c) + S(c,il) + 5 OjCg) + 5H2(g) = V0S0^•5H20(a,c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(C- H°,8)/T 


H°- HUs 


AHf 


AGf 


298.15 


76.000 


73.500 


73.500 





-676.690 


-574.682 


421.248 


300 


76.333 


73.971 


73.501 


.141 


-676.700 


-574.049 


418.189 


350 


85.333 


86.414 


74.463 


4.183 


-676.734 


-556.931 


347.759 


368.30 


88.627 


90.847 


75.167 


5.775 


-676.646 


-550.669 


326.764 


368.30 


88.627 


90.847 


75.167 


5.775 


-676.742 


-550.669 


326.764 


388.36 


92.238 


95.641 


76.102 


7.588 


-676.588 


-543.806 


306.023 


388.36 


92.238 


95.641 


76.102 


7.588 


-677.001 


-543.806 


306.023 


400 


94.333 


98.396 


76.711 


8.674 


-676.900 


-539.816 


294.938 


432.02 


100.097 


105.879 


78.595 


11.787 


-676.527 


-528.855 


267.533 


450 


103.333 


110.026 


79.768 


13.616 


-676.319 


-522.714 


253.861 


500 


112.333 


121.379 


83.363 


19.008 


-675.289 


-505.697 


221.037 


550 


121.333 


132.508 


87.328 


24.849 


-673.828 


-488.805 


194.231 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 

Sources: The enthalpy of formation at 298 K is based on Reggiani (41 ). The 
entropy at 298 K and the heat capacities are estimates. 



15 



TABLE 5. - Thermodynamic properties of V0S0,j»5H20(e,c) 
[Formation: V(c) + S(c,£) + 5 OjCg) + SHjCg) = VOSO^'SHjOCe.c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp» 


S" 


-(C- H$,8)/T 


H'- Hjse 


AHf 


AGf 


298.15 


76.000 


73.500 


73.500 





-676.200 


-574.192 


420.889 


300 


76.333 


73.971 


73.501 


.141 


-676.210 


-573.559 


417.832 


350 


85.333 


86.414 


74.463 


4.183 


-676.244 


-556.441 


347.453 


368.30 


88.627 


90.847 


75.167 


5.775 


-676.156 


-550.179 


326.473 


368.30 


88.627 


90.847 


75.167 


5.775 


-676.253 


-550.179 


326.473 


388.36 


92.238 


95.641 


76.102 


7.588 


-676.098 


-543.316 


305.748 


388.36 


92.238 


95.641 


76.102 


7.588 


-676.511 


-543.316 


305.748 


400 


94.333 


98.396 


76.711 


8.674 


-676.410 


-539.326 


294.670 


432.02 


100.097 


105.879 


78.595 


11.787 


-676.037 


-528.365 


267.285 


450 


103.333 


110.026 


79.768 


13.616 


-675.829 


-522.224 


253.623 


500 


112.333 


121.379 


83.363 


19.008 


-674. 799 


-505.207 


220.823 


550 


121.333 


132.508 


87.328 


24.849 


-673.338 


-488.315 


194.036 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH' 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



0.096 kcal/mol. 



Sources: The enthalpy of formation at 298 K is based on Reggiani (41). 
entropy at 298 K and the heat capacities are estimates. 



The 



TABLE 6. - Thermodynamic properties of V0S0i,*6H20(c) 
[Formation: V(c) + S(c,«,) + 5.5 02(g) + 6H2(g) = V0S0^•6H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- H°,«)/T 


H°- H|,8 


AHf 


AGf 


298.15 


85.000 


83.000 


83.000 





-746.920 


-631.135 


462.628 


300 


85.388 


83.527 


83.000 


.158 


-746.932 


-630.416 


459.252 


350 


95.888 


97.478 


84.078 


4.690 


-746.998 


-610.984 


381.511 


368.30 


99.731 


102.463 


84.869 


6.480 


-746.905 


-603.874 


358.335 


368.30 


99.731 


102.463 


84.869 


6.480 


-747.001 


-603.874 


358.335 


388.36 


103.944 


107.862 


85.919 


8.522 


-746.830 


-596.083 


335.442 


388.36 


103.944 


107.862 


85.919 


8.522 


-747.243 


-596.083 


335.442 


400 


106.388 


110.968 


86.603 


9.746 


-747.127 


-591.554 


323.206 


432.02 


113.112 


119.416 


88.722 


13.260 


-746.691 


-579.116 


292.959 


450 


116.888 


124.105 


90.043 


15.328 


-746.437 


-572.148 


277.870 


500 


127.388 


136.964 


94.094 


21.435 


-745.225 


-552.842 


241.644 


550 


137.889 


149.597 


98.566 


28.067 


-743.510 


-533.681 


212.063 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 



Sources; The enthalpy of formation at 298 K is based on Reggiani (41), 
entropy at 298 K and the heat capacities are estimates. 



The 



16 



TABLE 7. - Thermodynamic properties of Cr2(S0i,)3 (c) 
[Formation: 2Cr(c) + 3S(c,Jl) + 6 OjCg) = C^2(S0^)3 (c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- H|98)/T 


H"- H2%8 


AHf 


AGf° 


298.15 


67.250 


61.850 


61.850 





-705.000 


-625.554 


458.538 


300 


67.458 


62.267 


61.850 


0.125 


-705.003 


-625.061 


455.351 


311.50 


68.655 


64.827 


61.913 


0.908 


-705.028 


-621.996 


436.390 


368.30 


74.565 


76.844 


63.301 


4.988 


-704.951 


-606.857 


360.106 


368.30 


74.565 


76.844 


63.301 


4.988 


-705.239 


-606.857 


360.106 


388.36 


76.653 


80.855 


64.106 


6.505 


-705.198 


-601.498 


338.489 


388.36 


76.653 


80.855 


64.106 


6.505 


-706.437 


-601.498 


338.490 


400 


77.864 


83.137 


64.627 


7.404 


-706.446 


-598.354 


326.921 


432.02 


80.675 


89.241 


66.228 


9.942 


-706.476 


-589.702 


298.314 


500 


86.643 


101.485 


70.199 


15.643 


-706.648 


-571.292 


249.708 


600 


93.796 


117.939 


76.807 


24.679 


-706.029 


-544.264 


198.245 


700 


99.322 


132.834 


83.765 


34.348 


-704.802 


-517.391 


161.535 


717.82 


100.017 


135.340 


85.015 


36.124 


-704.532 


-512.622 


156.073 



Phase changes; 



Sources: 



0.096 kcal/mol. 



311.5 K, second-order transition for Cr; AH° = kcal/mol. 
368.3 K, orthorhombic-monoclinic transformation of S; Ah° 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 

The enthalpy of formation at 298 K is based on Jacob (18). The entropy at 298 K is 
from Kubaschewski (28). The heat capacity at 298 K is from Vasileff (45). The 
high-temperature enthalpy values are estimates. 



TABLE 8. - Thermodynamic properties of C^2(S0^)3(c) 
[Formation: 2Cr(c) + 1.5S2(g) + 6 02(g) = Cr2(S0H )$ (c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(C- HS9e)/T 


H°- H^ss 


AHf 


AGf 


298.15 


67.250 


61.850 


61.850 





-751.065 


-654.095 


479.458 


300 


67.458 


62.267 


61.850 


.125 


-751.059 


-653.493 


476.063 


311.50 


68.655 


64.827 


61.913 


.908 


-751.030 


-649.753 


455.864 


400 


77.864 


83.137 


64.627 


7.404 


-750.399 


-621.051 


339.322 


500 


86.643 


101.485 


70.199 


15.643 


-749.031 


-588.852 


257.384 


600 


93.796 


117.939 


76.807 


24.679 


-747.112 


-556.986 


202.880 


700 


99.322 


132.834 


83.765 


34.348 


-744.777 


-525.476 


164.059 


800 


103.222 


146.369 


90.758 


44.489 


-742.154 


-494.329 


135.043 


900 


105.495 


158.674 


97.632 


54.938 


-739.370 


-463.517 


112.556 



Phase change 
Sources: 



311.5 K, second-order transition for Cr; Ah" = kcal/mol. 



The enthalpy of formation at 298 K is based on Jacob (18). The entropy at 

298 K is from Kubaschewski (28). The heat capacity at 298 K is from Vasileff (45), 

The high-temperature enthalpy values are estimates. 



17 



TABLE 9. - Thermodynamic properties of [Cr2(H20)6(S0^)3 ]*2H20(c) 
[Formation: 2Cr(c) + 3S(c,Jl) + 10 OjCg) + SHjCg) - [Cr2(H20)6(S0.,)3]*2H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S° 


-(C- wUt)n 


H"- Hlse 


AHf 


AGf 


298.15 


141.000 


138.000 


138.000 





-1302.500 


-1112.880 


815.752 


300 


141.536 


138.874 


138.004 


.261 


-1302.523 


-1111.705 


809.866 


311.50 


144.871 


144.261 


138.136 


1.908 


-1302.642 


-1104.387 


774.833 


350 


156.036 


161.781 


139.778 


7.701 


-1302.907 


-1079.863 


674.288 


368.30 


161.343 


169.869 


141.074 


10.605 


-1302.707 


-1068.215 


633.873 


368.30 


161.343 


169.869 


141.074 


10.605 


-1302.995 


-1068.215 


633.873 


388.36 


167.160 


178.577 


142.786 


13.900 


-1302.867 


-1055.428 


593.935 


388.36 


167.160 


178.577 


142.786 


13.900 


-1304.106 


-1055.428 


593.936 


400 


170.536 


183.563 


143.901 


15.865 


-1304.033 


-1047.977 


572.581 


432.02 


179.822 


197.047 


147.341 


21.474 


-1303.706 


-1027.492 


519.780 


450 


185.036 


204.486 


149.477 


24.754 


-1303.633 


-1015.995 


493.428 


500 


199.536 


224.732 


155.994 


34.369 


-1302.486 


-984.087 


430.139 


550 


214.036 


244.430 


163.143 


44.708 


-1300.649 


-952.329 


378.416 



Phase changes ; 311.5 K, second-order transition for Cr; AH° = kcal/mol. 
368.3 K, orthorhombic-monoclinic transformation of S; AH" 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



0.096 kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48). 
capacities are estimates. 



The entropy at 298 K and heat 



TABLE 10. - Thermodynamic properties of [Cr(H20)6]2(S0^) j*2H20(c) 
[Formation: 2Cr(c) + 3S(c,)l) + 13 02(g) + 14H2(g) = [Cr(H20)6 ]2(S0^)3»2H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(c- wu^)n 


L|0 ijO 

M - 0298 


AHf 


AGf 


298.15 


197.000 


195.000 


195.000 





-1732.000 


-1459.716 


1069.987 


300 


197.925 


196.221 


195.004 


.365 


-1732.036 


-1458.028 


1062.159 


311.50 


203.675 


203.774 


195.190 


2.674 


-1732.212 


-1447.520 


1015.574 


350 


222.925 


228.609 


197.503 


10.887 


-1732.473 


-1412.309 


881.874 


368.30 


232.075 


240.203 


199.339 


15.050 


-1732.167 


-1395.585 


828.132 


368.30 


232.075 


240.203 


199.339 


15.050 


-1732.455 


-1395.585 


828.132 


388.36 


242.105 


252.773 


201.774 


19.806 


-1732.134 


-1377.242 


775.034 


388.36 


242.105 


252.773 


201.774 


19.806 


-1733.373 


-1377.242 


775.034 


400 


247.925 


260.009 


203.364 


22.658 


-1733.151 


-1366.573 


746.651 


432.02 


263.935 


279.708 


208.293 


30.853 


-1732.274 


-1337.260 


676.483 


450 


272.925 


290.653 


21 1 . 366 


35.679 


-1731.804 


-1320.828 


641.473 


500 


297.925 


320.703 


220.803 


49.950 


-1729.203 


-1275.291 


557.422 


550 


322.925 


350.271 


231.231 


65.472 


-1725.405 


-1230.071 


488.779 



Phase changes ; 311.5 K, second-order transition for Cr; AH° = kcal/mol. 

368.3 K, orthorhombic-monoclinic transformation of S; Ah° = 0.096 kcal/mol. 

388.36 K, melting point of S; AH° = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; Ah° = kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48), 
capacities are estimates. 



The entropy at 298 K and heat 



18 



TABLE 11. - Thermodynamic properties of [Cr(H20)j]2(S0^)3*3H20(c) 
[Formation: 2Cr(c) + 3S(c,A) + 13.5 O^ig) + ISHjCg) = [Cr(H20)j]2(S0,,)3*3H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- H29b)/T 


H - Hjse 


AHf 


AGf 


298.15 


206.000 


204.000 


204.000 





-1802.100 


-1515.889 


1111.162 


300 


206.999 


205.277 


204.004 


.382 


-1802.139 


-1514.115 


1103.018 


311.50 


213.209 


213.180 


204.197 


2.798 


-1802.327 


-1503.070 


1054.547 


350 


233.999 


239.214 


206.623 


11.407 


-1802.595 


-1466.057 


915.436 


368.30 


243.881 


251.391 


208.547 


15.780 


-1802.272 


-1448.478 


859.518 


368.30 


243.881 


251.391 


208.547 


15.780 


-1802.560 


-1448.478 


859.519 


388.36 


254.713 


264.608 


211.100 


20.781 


-1802.205 


-1429.198 


804.272 


388.36 


254.713 


264.608 


211.100 


20.781 


-1803.444 


-1429.198 


804.272 


400 


260.999 


272.223 


212.768 


23.782 


-1803.195 


-1417.986 


774.741 


432.02 


278.290 


292.978 


217.944 


32.416 


-1802.218 


-1387.186 


701.739 


450 


287.999 


304.523 


221.174 


37.507 


-1801.675 


-1369.922 


665.316 


500 


314.999 


336.264 


231.100 


52.582 


-1798.804 


-1322.089 


577.877 


550 


341.999 


367.553 


242.086 


69.007 


-1794.640 


-1274.606 


506.475 



Phase changes ; 311.5 K, second-order transition for Cr; AH" = kcal/mol. 

368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 

388.36 K, melting point of S; AH" = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH° = kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48). 
capacities are estimates. 



The entropy at 298 K and heat 



TABLE 12. - Thermodynamic properties of [Cr(H20)e]2(S0^)3'4H20(c) 
[Formation: 2Cr(c) + 3S(c,il) + 14 02(g) + 16H2(g) = [Cr(H20)e]2(S0^)3'4H20(c) 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cpo 


S" 


-(G"- H^9e)/T 


M - M298 


AHf 


AGf 


298.15 


216.000 


214.000 


214.000 





-1871.300 


-1571.461 


1151.897 


300 


217.073 


215.339 


214.002 


.401 


-1871.339 


-1569.601 


1143.439 


311.50 


223.743 


223.630 


214.206 


2.936 


-1871.529 


-1558.031 


1093.108 


350 


246.073 


250.979 


216.753 


11.979 


-1871.765 


-1519.260 


948.656 


368.30 


256.687 


263.790 


218.775 


16.579 


-1871.407 


-1500.847 


890.594 


368.30 


256.687 


263.790 


218.775 


16.579 


-1871.695 


-1500.847 


890.594 


388.36 


268.322 


277.707 


221.457 


21.845 


-1871.286 


-1480.655 


833.229 


388.36 


268.322 


277.707 


221.457 


21.845 


-1872.525 


-1480.655 


833.229 


400 


275.073 


285.731 


223.211 


25.008 


-1872.238 


-1468.915 


802.567 


432.02 


293.645 


307.618 


228.655 


34.114 


-1871.128 


-1436.669 


726.771 


450 


304.073 


319.804 


232.055 


39.487 


-1870.494 


-1418.599 


688.957 


500 


333.073 


353.342 


242.512 


55.415 


-1867.304 


-1368.544 


598.183 


550 


362.073 


386.448 


254.095 


72.794 


-1862.723 


-1318.877 


524.067 



Phase changes ; 311.5 K, second-order transtion for Cr; ^H" = kcal/mol. 
368.3 K, orthorhombic-monoclinic transformation of S; Ah° 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah° = kcal/mol. 



0.096 kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48), 
capacities are estimates. 



The entropy at 298 K and heat 



19 



TABLE 13. - Thermodynamic properties of [C^(H20)s]2(S0^) j»5H20(c) 
[Formation: 2Cr(c) + 3S(c,]l) + 14.5 OjCg) + ITHjCg) = [Cr(H20)s]2(S0.^)j'5H20(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- HUb)/T 


H"- Hjse 


AHf 


AGf 


298.15 


225.000 


223.000 


223.000 





-1940.700 


-1626.934 


1192.560 


300 


226.128 


224.395 


223.005 


.417 


-1940.742 


-1624.989 


1183.789 


311.50 


233.143 


233.033 


223.217 


3.058 


-1940.946 


-1612.881 


1131.590 


350 


256.629 


261.544 


225.870 


12.486 


-1941.200 


-1572.308 


981.780 


368.30 


267.792 


274.907 


227.977 


17.284 


-1940.836 


-1553.038 


921.563 


368.30 


267.792 


274.907 


227.977 


17.284 


-1941.124 


-1553.038 


921.564 


388.36 


280.029 


289.428 


230.774 


22.779 


-1940.698 


-1531.907 


862.071 


388.36 


280.029 


289.428 


230.774 


22.779 


-1941.937 


-1531.907 


862.071 


400 


287.129 


297.803 


232.603 


26.080 


-1941.635 


-1519.623 


830.273 


432.02 


306.661 


320.654 


238.281 


35.587 


-1940.463 


-1485.884 


751.668 


450 


317.629 


333.382 


241.829 


41.199 


-1939.781 


-1466.977 


712.452 


500 


348.129 


368.426 


252.740 


57.843 


-1936.409 


-1414.608 


618.317 


550 


378.629 


403.037 


264.833 


76.012 


-1931.575 


-1362.649 


541.460 



Phase changes ; 311.5 K, second-order transition for Cr; AH° = kcal/mol. 

368.3 K, orthorhombic-monoclinic transformation of S; Ah° = 0.096 kcal/mol. 

388.36 K, melting point of S; Ah° r 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH" = kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48). 
capacities are estimates. 



The entropy at 298 K and heat 



TABLE 14. - Thermodynamic properties of MnS0^(c) 
[Formation: Mn(c) + S(c,A) + 2 OjCg) = MnSO,j(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp' 


S" 


-(G"- HU,)/J 


H°- HUi_ 


AHf° 


AGf° 


298.15 


24.020 


26.790 


26.790 





-254.700 


-228.901 


167.787 


300 


24.110 


26.939 


26.789 


.045 


-254.703 


-228.740 


166.635 


368.30 


26.780 


32.208 


27.314 


1.802 


-254.735 


-222.825 


132.223 


368.30 


26.780 


32.208 


27.314 


1.802 


-254.831 


-222.825 


132.223 


388.36 


27.564 


33.649 


27.605 


2.348 


-254.826 


-221.081 


124.412 


388.36 


27.564 


33.649 


27.605 


2.348 


-255.239 


-221.081 


124.412 


400 


28.019 


34.470 


27.793 


2.671 


-255.249 


-220.057 


120.232 


432.02 


28.859 


36.660 


28.370 


3.582 


-255.283 


-217.240 


109.896 


500 


30.643 


41.018 


29.796 


5.611 


-255.406 


-211.236 


92.330 


600 


32.674 


46.791 


32.158 


8.780 


-255.346 


-202.405 


73.725 


700 


34.313 


51.956 


34.623 


12.133 


-255.131 


-193.600 


60.444 


717.82 


34.550 


52.822 


35.064 


12.747 


-255.079 


-192.033 


58.466 



Phase changes ; 



Sources; 



368.3 K, orthorhombic-monoclinic transformation of S; Ah° = 0.096 kcal/mol. 

388.36 K, melting point of S; Ah" = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; Ah" = kcal/mol. 

717.824 K, boiling point of S to equilibrium mixture. 

The enthalpy of formation at 298 K is taken from Southard (42), corrected for sulfate 
ion CODATA (8) value. The entropy at 298 K and low-temperature heat capacities are 
from Moore (34). The high temperature enthalpy data are from Southard (42). 



20 



TABLE 15. - Thermodynamic properties of MnSOi,(c) 
[Formation: Mn(c) + 0.5S2(g) + 2 OjCg) = MnSO^(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


5" 


-(C- H|,8)/T 


mO mO 

M - Haae 


AHf 


AGf 


298.15 


24.020 


26.790 


26.790 





-270.055 


-238.414 


174.760 


300 


24.110 


26.939 


26.789 


.045 


-270.055 


-238.217 


173.539 


400 


28.019 


34.470 


27.793 


2.671 


-269.900 


-227.623 


124.366 


500 


30.643 


41.018 


29.796 


5.611 


-269.534 


-217.089 


94.888 


600 


32.674 


46.791 


32.158 


8.780 


-269.040 


-206.646 


75.270 


700 


34.313 


51.956 


34.623 


12.133 


-268.456 


-196.295 


61.285 


800 


35.642 


56.627 


37.086 


15.633 


-267.806 


-186.032 


50.821 


900 


36.702 


60.889 


39.498 


19.252 


-267.104 


-175.853 


42.703 


980 


37.350 


64.044 


41.374 


22.216 


-266.516 


-167.763 


37.412 


980 


37.350 


64.044 


41 . 374 


22.216 


-267.048 


-167.763 


37.412 


1000 


37.512 


64.800 


41.835 


22.965 


-266.901 


-165.743 


36.223 


1100 


38.085 


68.404 


44.089 


26.747 


-266.150 


-155.653 


30.925 



Phase change ; 980 K, a-6 transition of Mn; AH° = 0.532 kcal/mol. 

Sources: The enthalpy of formation at 298 K is from Southard (42), corrected for sulfate ion 
CODATA (8^) value. The entropy at 298 K and low-temperature heat capacities are from 
Moore (34). The high-temperature enthalpy data are from Southard (42). 



TABLE 16. - Thermodynamic properties of MnS0^•H20(a,c) 
[Formation: Mn(c) + S(c,A) + 2.5 02(g) + H2(g) = MnS0^•H20(a,c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(C- H598)/T 


H"- H29e 


AHf° 


AGf 


298.15 


33.000 


35.000 


35.000 





-329.100 


-289.139 


211.942 


300 


33.167 


35.205 


35.002 


.061 


-329.107 


-288.891 


210.454 


350 


37.667 


40.655 


35.421 


1.832 


-329.161 


-282.182 


176.200 


368.30 


39.314 


42.617 


35.730 


2.536 


-329.135 


-279.726 


165.988 


368.30 


39.314 


42.617 


35.730 


2.536 


-329.231 


-279.726 


165.988 


388.36 


41.120 


44.749 


36.141 


3.343 


-329.176 


-277.030 


155.897 


388.36 


41.120 


44.749 


36.141 


3.343 


-329.589 


-277.030 


155.897 


400 


42.168 


45.979 


36.409 


3.828 


-329.561 


-275.456 


150.500 


432.02 


45.050 


49.335 


37.242 


5.224 


-329.448 


-271.129 


137.157 


450 


46.669 


51.205 


37.763 


6.049 


-329.423 


-268.700 


130.497 


500 


51.169 


56.355 


39.365 


8.495 


-329.055 


-261.970 


114.505 


550 


55.670 


61.443 


41.141 


11.166 


-328.472 


-255.288 


101.441 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 

Sources: The enthalpy of formation at 298 K is from Wagman (48) corrected for sulfate ion 
CODATA (8) value. The entropy at 298 K and heat capacities are estimates. 



21 



TABLE 17. - Thermodynamic properties of MnS0i,*4H20(c) 
[Formation: Mn(c) + S(c,A) + 4 OjCg) + 4H2(g) = MnS0^•4H20(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- HU,)/1 


H"- Hl„ 


AHf 


AGf 


298.15 


61.000 


65.000 


65.000 





-539.800 


-458.954 


336.418 


300 


61.266 


65.378 


65.001 


.113 


-539.813 


-458.452 


333.978 


350 


68.467 


75.363 


65.774 


3.356 


-539.963 


-444.877 


277.790 


368.30 


71.103 


78.920 


66.340 


4.633 


-539.941 


-439.905 


261.037 


368.30 


71.103 


78.920 


66. 340 


4.633 


-540.037 


-439.905 


261.037 


388.36 


73.992 


82.766 


67.087 


6.089 


-539.967 


-434.452 


244.485 


388.36 


73.992 


82.766 


67.087 


6.089 


-540.380 


-434.452 


244.485 


400 


75.668 


84.976 


67.576 


6.960 


-540.334 


-431.278 


235.636 


432.02 


80.280 


90.978 


69.089 


9.456 


-540.140 


-422.555 


213.759 


450 


82.869 


94.304 


70.031 


10.923 


-540.047 


-417.662 


202.842 


500 


90.069 


103.408 


72.914 


15.247 


-539.402 


-404.093 


176.627 


550 


97.270 


112.330 


76.094 


19.930 


-538.418 


-390.609 


155.212 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 

Sources: The enthalpy of formation at 298 K is from Wagman (48), corrected for sulfate ion 
CODATA (8) value. The entropy at 298 K and heat capacities are estimates. 



TABLE 18. - Thermodynamic properties of MnS0^•5H20(c) 
[Formation: Mn(c) + S(c,il) + 4.5 02(g) + 5H2(g) = MnS0^*5H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(C- HUJ/1 


H"- H|,8 


AHf 


AGf° 


298.15 


78.000 


75.000 


75.000 





-610.300 


-515.826 


378.105 


300 


78.333 


75.484 


75.001 


.145 


-610.300 


-515.239 


375.347 


350 


87.332 


88.234 


75.988 


4.286 


-610.075 


-499.408 


311.841 


368.30 


90.626 


92.769 


76.710 


5.914 


-609.894 


-493.626 


292.915 


368.30 


90.626 


92.769 


76.710 


5.914 


-609.990 


-493.627 


292.915 


388.36 


94.237 


97.670 


77.666 


7.769 


-609.732 


-487.294 


274.221 


388.36 


94.237 


97.670 


77.666 


7.769 


-610.145 


-487.294 


274.222 


400 


96.332 


100.484 


78.289 


8.878 


-609.984 


-483.614 


264.231 


432.02 


102.095 


108.120 


80.218 


12.054 


-609.449 


-473.519 


239.540 


450.00 


105.331 


112.349 


81.418 


13.919 


-609.151 


-467.866 


227.224 


500 


114.331 


123.913 


85.091 


19.411 


-607.871 


-452.232 


197.668 


550 


123.330 


135.232 


89.137 


25.352 


-606.166 


-436.748 


173.546 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° r kcal/mol. 

Sources: The enthalpy of formation at 298 K is from Wagman (48), corrected for sulfate ion 

CODATA (8^) value. The entropy at 298 K is estimated. The heat capacity at 298 K is 
from Wagman (48). 



22 



TABLE 19. - Thermodynamic properties of MnS0i,*7H20(c) 
[Formation: Mn(c) + S(c,i) + 5.5 OjCg) + THjCg) = MnSO^'THjOCc)] 



T, K 


cal/mol'K 


kcal/mol ' 


1 «-»«t i/r 


Cp" 


S° 


-(C- H2,8)/T 


n - "2 9 8 


AHf° 


AGf 




298.15 


91.000 


94.000 


94.000 





-750.400 


-628.371 


460.602 


300 


91.444 


94.564 


94.001 


.169 


-750.416 


-627.613 


457.210 


350 


103.443 


109.562 


95.159 


5.041 


-750.504 


-607.132 


379.105 


368.30 


107.835 


114.946 


96.010 


6.974 


-750.403 


-599.638 


355.822 


368.30 


107.835 


114.946 


96.010 


6.974 


-750.499 


-599.638 


355.822 


388.36 


112.649 


120.790 


97.138 


9.186 


-750.307 


-591.425 


332.820 


388.36 


112.649 


120.790 


97.138 


9.186 


-750.720 


-591.425 


332.820 


400 


115.442 


124.158 


97.875 


10.513 


-750.587 


-586.653 


320.528 


432.02 


123.127 


133.339 


100.164 


14.332 


-750.087 


-573.548 


290.142 


450 


127.442 


138.448 


101.592 


16.585 


-749.783 


-566.206 


274.984 


500 


139.441 


152.496 


105.982 


23.257 


-748.391 


-545.877 


238.599 


550 


151.440 


166.349 


110.842 


30.529 


-746.429 


-525.717 


208.898 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; Ah° = 0.096 kcal/mol. 
388.36 K, melting point of S; Ah° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 

Sources: The enthalpy of formation at 298 K is from Wagman (48), corrected for sulfate ion 
CODATA (8) value. The entropy at 298 K and heat capacities are estimates. 



TABLE 20. - Thermodynamic properties of FeSO^(c) 
[Formation: Fe(c) + S(c,il) + 2 02(g) = FeSOH(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S° 


-(G°- H|98)/T 


n - "298 


AHf° 


AGf° 











00 


-4.008 


-220.529 


-220.529 


00 


100 


10.534 


10.223 


46.563 


-3.634 


-221.810 


-214.108 


467.926 


200 


18.845 


20.319 


30.964 


-2.129 


-222.512 


-206.098 


225.211 


298.15 


24.040 


28.909 


28.909 





-222.800 


-197.969 


145.114 


300 


24.140 


29.058 


28.908 


.045 


-222.802 


-197.814 


144.106 


368.30 


26.694 


34.282 


29.430 


1.787 


-222.831 


-192.122 


114.004 


368.30 


26.694 


34.282 


29.430 


1.787 


-222.927 


-192.122 


114.004 


388.36 


27.445 


35.718 


29.718 


2.330 


-222.919 


-190.443 


107.171 


388.36 


27.445 


35.718 


29.718 


2.330 


-223.332 


-190.444 


107.171 


400 


27.880 


36.535 


29.905 


2.652 


-223.341 


-189.458 


103.514 


432.02 


28.818 


38.718 


30.478 


3.560 


-223.372 


-186.745 


94.469 


500 


30.810 


43.085 


31.899 


5.593 


-223.481 


-180.968 


79.100 


600 


32.990 


48.904 


34.257 


8.788 


-223.390 


-172.469 


62.821 


700 


34.570 


54.113 


36.727 


12.170 


-223.159 


-163.998 


51.202 


717.82 


34.773 


54.985 


37.170 


12.788 


-223.108 


-162.492 


49.472 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 



Sources: Enthalpy of formation at 298 K is based on Wagman (48). 
at 298 K are from JANAF (10). 



Heat capacities and entropy 



23 



TABLE 21. - Thermodynamic properties of FeSOi,(c) 
[Formation: Fe(c) + O.SSjCg) + 2 OjCg) = FeSO^(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp« 


S° 


-(C- H598)/T 


LfO ijO 

n - H2 9 8 


AHf 


AGf° 











00 


-4.008 


-235.847 


-235.847 


oo 


100 


10.534 


10.223 


46.563 


-3.634 


-237.331 


-227.598 


497.408 


200 


18.845 


20.319 


30.964 


-2.129 


-237.995 


-217.560 


237.735 


298.15 


24.040 


28.909 


28.909 





-238.155 


-207.483 


152.087 


300 


24.140 


29.058 


28.908 


.045 


-238.154 


-207.292 


151.010 


400 


27.880 


36.535 


29.905 


2.652 


-237.992 


-197.023 


107.647 


500 


30.810 


43.085 


31.899 


5.593 


-237.609 


-186.821 


81.658 


600 


32.990 


48.904 


34.257 


8.788 


-237.085 


-176.710 


64.366 


700 


34.570 


54.113 


36.727 


12.170 


-236.484 


-166.693 


52.043 


800 


35.710 


58.808 


39.199 


15.687 


-235.864 


-156.768 


42.826 


900 


36.510 


63.061 


41.618 


19.299 


-235.282 


-146.916 


35.676 


1000 


37.160 


66.943 


43.960 


22.983 


-234.831 


-137.126 


29.968 


1043 


37.396 


68.512 


44.940 


24.586 


-234.773 


-132.926 


27.853 


1100 


37.710 


70.511 


46.214 


26.727 


-234.544 


-127.364 


25.305 


1185 


38.126 


73.333 


48.058 


29.951 


-234.029 


-119.100 


21.965 


1185 


38.126 


73.333 


48.058 


29.951 


-234.244 


-119.099 


21.965 


1200 


38.200 


73.813 


48.377 


30.523 


-234.117 


-117.644 


21.426 


1300 


38.640 


76.889 


50.454 


34.365 


-233.261 


-107.974 


18.152 


1400 


39.040 


79.767 


52.446 


38.250 


-232.404 


-98.367 


15.356 


1500 


39.420 


82.473 


54.358 


42.173 


-231.544 


-88.824 


12.941 


1600 


39.780 


85.029 


56.196 


46.133 


-230.684 


-79.337 


10.837 


1667 


40.008 


86.666 


57.388 


48.806 


-230.108 


-73.011 


9.572 


1667 


40.008 


86.666 


57.388 


48.806 


-230.308 


-73.011 


9.572 


1700 


40.120 


87.451 


57.964 


50.128 


-230.050 


-69.900 


8.986 


1800 


40.460 


89.754 


59.667 


54.157 


-229.269 


-60.500 


7.346 


1811 


40.495 


90.001 


59.850 


54.602 


-229.186 


-59.472 


7.177 


1811 


40.495 


90.001 


59.850 


54.602 


-232.486 


-59.472 


7.177 


1900 


40. 780 


91.950 


61.308 


58.219 


-231.864 


-50.985 


5.865 


2000 


41.100 


94.050 


62.894 


62.313 


-231.146 


-41.484 


4.533 



Phase changes : 1043 K, Curie temperature of Fe; Ah° = kcal/mol. 

1185 K, a-Y transition point of Fe; AH" = 0.215 kcal/mol. 

1667 K, Y-6 transition point of Fe; AH° = 0.200 kcal/mol. 

1811 K, melting point of Fe; AH° = 3.300 kcal/mol. 



Sources: Enthalpy of formation at 298 K is based on Wagman (48). 
at 298 K are from JANAF (10). 



Heat capacities and entropy 



24 



TABLE 22. - Thermodynamic properties of FeS0i,*H20(c) 
[Formation: Fe(c) + S(c,J.) + HjCg) + 2.5 OjCg) = FeS0^•H20(c)] 



T, K 


cal/mol»K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(0°- H°98)/T 


H"- H2%8 


AHf 


AGf 


298.15 


33.346 


37.700 


37.700 





-297.400 


-258.581 


189.542 


300 


33.513 


37.907 


37.700 


.062 


-297.404 


-258.339 


188.198 


350 


38.015 


43.411 


38.125 


1.850 


-297.429 


-251.825 


157.244 


368.30 


39.663 


45.390 


38.438 


2.561 


-297.391 


-249.441 


148.017 


368.30 


39.663 


45.390 


38.438 


2.561 


-297.487 


-249.441 


148.017 


388.36 


41.469 


47.541 


38.853 


3.374 


-297.420 


-246.825 


138.899 


388.36 


41.469 


47.541 


38.853 


3.374 


-297.833 


-246.825 


138.899 


400 


42.517 


48.781 


39.123 


3.863 


-297.798 


-245.297 


134.022 


432.02 


45.400 


52.165 


39.964 


5.271 


-297.668 


-241.099 


121.965 


450 


47.019 


54.049 


40.489 


6.102 


-297.634 


-238.745 


115.949 


500 


51.521 


59.236 


42.106 


8.565 


-297.242 


-232.221 


101.502 


550 


56.023 


64.357 


43.895 


11.254 


-296.636 


-225.744 


89.701 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 



Sources: Enthalpy of formation at 298 K is based on Adami (1). 
Pribylov (39). Heat capacities are estimates. 



The entropy at 298 K is from 



TABLE 23. - Thermodynamic properties of FeS0H*4H20(c) 
[Formation: Fe(c) + S(c,)l) + 4H2(g) + 4 02(g) = FeS0.,*4H20(c) ] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


cp- 


S" 


-(G°- H|9e)/T 


H"- H|,e 


AHf° 


AGf° 


298.15 


65.924 


67.500 


67.500 





-509.500 


-429.736 


315.001 


300 


66.190 


67.909 


67.502 


.122 


-509.503 


-429.241 


312.698 


350 


73.390 


78.653 


68.333 


3.612 


-509.392 


-415.868 


259.676 


368.30 


76.025 


82.460 


68.941 


4.979 


-509.276 


-410.981 


243.874 


368.30 


76.025 


82.460 


68.941 


4.979 


-509.372 


-410.981 


243.874 


388.36 


78.914 


86.567 


69.746 


6.533 


-509.198 


-405.625 


228.263 


388.36 


78.914 


86.567 


69.746 


6.533 


-509.612 


-405.625 


228.263 


400 


80.590 


88.922 


70.270 


7.461 


-509.506 


-402.510 


219.919 


432.02 


85.201 


95.303 


71.888 


10.116 


-509.147 


-393.958 


199.293 


450 


87.790 


98.830 


72.894 


11.671 


-508.963 


-389.169 


189.004 


500 


94.990 


108.452 


75.972 


16.240 


-508.066 


-375.903 


164.305 


550 


102.190 


117.844 


79.353 


21.170 


-506.830 


-362.743 


144.139 



Phase chanqes: 



0.096 kcal/mol. 



Sources: 



368.3 K, orthorhombic-monoclinic transformation of S; AH' 

388.36 K, melting point of S; AH° = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; Ah° = kcal/mol. 

717.824 K, boiling point of S to equilibrium mixture. 

Heat of formation at 298 K is based on Larson (29^). Entropy at 298 K is based on 
Malinin (32). Heat capacity at 298 K is from Kelley (21). 



25 



TABLE 24. - Thermodynamic properties of FeS0H*7H20(c) 
[Formation: Fe(c) + S(c,il) + IH^ig) + 5.5 OjCg) = FeSO^'THjOCc)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(G°- H|38)/T 


H - H29e 


AHf° 


AGf 


298.15 


94.313 


97.800 


97.800 





-720.440 


-599.881 


439.719 


300 


94.784 


98.385 


97.802 


.175 


-720.448 


-599.133 


436.462 


350 


107.210 


113.937 


99.003 


5.227 


-720.343 


-578.913 


361.485 


368.30 


111.543 


119.511 


99.884 


7.229 


-720.169 


-571.523 


339.138 


368.30 


111.543 


119.511 


99.884 


7.229 


-720.265 


-571.523 


339.138 


388.36 


116.293 


125.557 


101.053 


9.516 


-719.992 


-563.427 


317.065 


388.36 


116.293 


125.557 


101.053 


9.516 


-720.405 


-563.427 


317.065 


400 


119.049 


129.032 


101.817 


10.886 


-720.227 


-558.724 


305.269 


432.02 


126.254 


138.478 


104.185 


14.816 


-719.610 


-545.819 


276.115 


450 


130.300 


143.709 


105.660 


17.122 


-719.250 


-538.595 


261.574 


500 


140.964 


157.995 


110.183 


23.906 


-717.739 


-518.598 


226.676 


550 


151.040 


171.907 


115.163 


31.209 


-715.741 


-498.775 


198.192 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 

Sources: Enthalpy of formation at 298 K is based on Adami (J_). The entropy and heat capacity 
at 298 K are from Lyon (30). The high-temperature heat capacities are estimates. 



TABLE 25. - Thermodynamic properties of Fe2(S0i,)3 (c) 
[Formation: 2Fe(c) + 3S(c,A) + 6 OjCg) = Fe2(S0^)3(c) ] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(C- H29b)/T 


H - H298 


AHf 


AGf° 


298.15 


64.950 


67.550 


67.550 





-617.100 


-538.835 


394.971 


300 


65.207 


67.953 


67.553 


.120 


-617.110 


-538.348 


392.181 


368.30 


72.795 


82.213 


68.964 


4.880 


-617.242 


-520.395 


308.799 


368.30 


72.795 


82.213 


68.964 


4.880 


-617.530 


-520.395 


308.799 


388.36 


75.024 


86.134 


69.752 


6.362 


-617.523 


-515.103 


289.871 


388.36 


75.024 


86.134 


69.752 


6.362 


-618.762 


-515.103 


289.871 


400 


76.317 


88.369 


70.262 


7.243 


-618.799 


-511.997 


279.738 


432.02 


78.866 


94.344 


71.828 


9.727 


-618.918 


-503.444 


254.679 


500 


84.277 


106.287 


75.711 


15.288 


-619.315 


-485.227 


212.090 


600 


90.928 


122.255 


82.162 


24.056 


-619.122 


-458.415 


166.975 


700 


96.850 


136.724 


88.938 


33.450 


-618.586 


-431.681 


134.775 


717.82 


97.818 


139.171 


90.155 


35.184 


-618.204 


-426.928 


129.982 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; Ah° r 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah° = kcal/mol 
717.824 K, boiling point of S to equilibrium mixture. 



0.096 kcal/mol. 



Sources: Enthalpy of formation at 298 K is based on Barany (3). 
temperature enthalpy values are from Pankratz (37). 



The entropy and high- 



26 



TABLE 26. - Thermodynamic properties of Fe2(S0i,)3(c) 
[Formation: 2Fe(c) + 1.5S2(g) + 6 O^Cg) = Fe2(S0^)3(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cpo 


S" 


-(G°- H;,«)/T 




AHf» 


AGf 


298.15 


64.950 


67.550 


67.550 





-663.165 


-567.376 


415.892 


300 


65.207 


67.953 


67.553 


.120 


-663.166 


-566.780 


412.893 


400 


76.317 


88.369 


70.262 


7.243 


-662.752 


-534.693 


292.139 


500 


84.277 


106.287 


75.711 


15.288 


-661.697 


-502.787 


219.765 


600 


90.928 


122.255 


82.162 


24.056 


-660.206 


-471 . 1 38 


171.610 


700 


96.850 


136.724 


88.938 


33.450 


-658.361 


-439.766 


137.299 


800 


102.282 


150.015 


95.753 


43.410 


-656.226 


-408.687 


111.647 


800 


102.720 


150.643 


95.753 


43.912 


-655.724 


-408.687 


111.647 


900 


102.720 


162.742 


102.538 


54.184 


-653.579 


-377.939 


91.775 



Phase changes : 800 K, a-B transition point of Fe2(S0ij)3; AH" = 0.540 kcal/mol. 

Sources: Enthalpy of formation at 298 K is based on Barany (3). The entropy at 298 K and 
high-temperature enthalpy values are from Pankratz (37). 



TABLE 27. - Thermodynamic properties of CoSO^(c) 
[Formation: Co(c) + S(c,Jl) + 2 OjCg) = CoSO^(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- Hl,8)/T 


H°- HUe 


AHf 


AGf 











00 


-4.120 


-210.077 


-210.077 


00 


100 


10.625 


9.022 


46.032 


-3.701 


-211.334 


-203.474 


444.686 


\ 200 


19.188 


19.309 


30.144 


-2.167 


-212.042 


-195.303 


213.414 


298.15 


24.670 


28.060 


28.060 





-212.300 


-187.020 


137.087 


300 


24.773 


28.213 


28.060 


.046 


-212.301 


-186.861 


136.126 


368.30 


27.404 


33.608 


28.596 


1.846 


-212.266 


-181.076 


107.449 


368.30 


27.404 


33.608 


28.596 


1.846 


-212.362 


-181.076 


107.449 


388.36 


28.177 


35.082 


28.894 


2.403 


-212.336 


-179.372 


100.940 


388.36 


28.177 


35.082 


28.894 


2.403 


-212.749 


-179.372 


100.940 


400 


28.625 


35.921 


29.086 


2.734 


-212.747 


-178.372 


97.457 


432.02 


29.345 


38.153 


29.676 


3.662 


-212.750 


-175.621 


88.842 


500 


30.874 


42.568 


31.134 


5.717 


-212.818 


-169.763 


74.202 


600 


32.466 


48.344 


33.531 


8.888 


-212.706 


-161.159 


58.701 


700 


33.746 


53.447 


36.018 


12.200 


-212.478 


-152.585 


47.639 


700 


33.746 


53.447 


36.018 


12.200 


-212.586 


-152.585 


47.639 


717.82 


33.945 


54.298 


36.462 


12.803 


-212.532 


-151.061 


45.992 



Phase changes : 



Sources: 



368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 

388.36 K, melting point of S; AH° = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH° = kcal/mol. 

700 K, a-3 transition for Co(c); AH° = 0.108 kcal/mol. 

717.824 K, boiling point of S to equilibrium mixture. 

Enthalpy of formation at 298 K is based on Adami (J^). Entropy and low-temperature 
heat capacities are from Weller (50). The high-temperature heat capacities are 
estimates. 



27 



TABLE 28. - Thermodynamic properties of CoSOi,(c) 
[Formation: Co(c) + O.SSjCg) + 2 OjCg) = CoSO^(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(G°- HS,8)/T 




AHf° 


AGf° 











00 


-4.120 


-225.395 


-225.395 


00 


100 


10.625 


9.022 


46.032 


-3.701 


-226.855 


-216.964 


474.168 


200 


19.188 


19.309 


30.144 


-2.167 


-227.525 


-206.764 


225.939 


298.15 


24.670 


28.060 


28.060 





-227.655 


-196.533 


144.061 


300 


24.773 


28.213 


28.060 


.046 


-227.653 


-196.338 


143.030 


400 


28.625 


35.921 


29.086 


2.734 


-227.398 


-185.937 


101.590 


500 


30.874 


42.568 


31.134 


5.717 


-226.946 


-175.616 


76.761 


600 


32.466 


48.344 


33.531 


8.888 


-226.400 


-165.400 


60.246 


700 


33.746 


53.447 


36.018 


12.200 


-225.803 


-155.280 


48.480 


700 


33.746 


53.447 


36.018 


12.200 


-225.911 


-155.280 


48.480 


800 


34.861 


58.028 


38.488 


15.632 


-225.262 


-145.234 


39.676 


900 


35.880 


62.193 


40.894 


19.169 


-224.593 


-135.272 


32.848 


964 


36.500 


64.679 


42.392 


21.485 


-224.156 


-128.945 


29.233 


964 


36.495 


65.213 


42.392 


22.000 


-223.641 


-128.945 


29.233 


1000 


36.837 


66.557 


43.237 


23.320 


-223.394 


-125.413 


27.409 


1100 


37.759 


70.112 


45.521 


27.050 


-222.706 


-115.640 


22.975 


1200 


38.653 


73.436 


47.710 


30.871 


-222.023 


-105.938 


19.294 


1300 


39.528 


76.564 


49.810 


34.780 


-221.372 


-96.295 


16.188 


1394 


40.336 


79.352 


51.709 


38.534 


-220.839 


-87.278 




1400 


40.388 


79.525 


51.828 


38.776 


-220.798 


-86.703 


13.535 



Phase changes ; 700 K, a-3 transition for Co(c); AH° = 0.108 kcal/mol. 

964 K, a-B transition of CoSO^Cc); AH° = 0.515 kcal/mol. 
1394 K, Curie temperature of Co(c); AH°= kcal/mol. 

Sources: Enthalpy of formation at 298 K is based on Adami (1). Entropy and low-temperature 

heat capacities are from Weller (50). High-temperature heat capacities are estimates. 



TABLE 29. - Thermodynamic properties of CoS0^*H20(c) 
[Formation: Co(c) + S(c,£) + 2.5 02(g) + H2(g) = CoS0^»H20(c)] 



T, K 


cal/mol"K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- H|,J/T 


H°- H2%8 


AHf 


AGf 


298.15 


34.000 


42.000 


42.000 





-286.800 


-239.762 


175.748 


300 


34.170 


42.211 


42.001 


.063 


-286.816 


-239.469 


174.450 


350 


38.668 


47.816 


42.433 


1.884 


-287.150 


-231.553 


144.586 


368.30 


40.314 


49.829 


42.751 


2.607 


-287.225 


-228.644 


135.676 


368.30 


40.314 


49.829 


42.751 


2.607 


-287.321 


-228.644 


135.676 


388.36 


42.118 


52.014 


43.172 


3.434 


-287.377 


-225.445 


126.868 


388.36 


42.118 


52.014 


43.172 


3.434 


-287.790 


-225.446 


126.868 


400 


43.165 


53.273 


43.448 


3.930 


-287.827 


-223.577 


122.155 


432.02 


46.045 


56.707 


44.305 


5.358 


-287.893 


-218.431 


110.498 


450 


47.662 


58.617 


44.839 


6.200 


-287.970 


-215.534 


104.676 


500 


52.159 


63.871 


46.479 


8.696 


-287.878 


-207.488 


90.692 


550 


56.656 


69.053 


48.297 


11.416 


-287.572 


-199.462 


79.258 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



Sources: Enthalpy of formation at 298 K is based on Goldberg (15), 
from Goldberg (15). Heat capacities are estimates. 



The entropy at 298 K is 



28 



TABLE 30. - Thermodynamic properties of CoS0i,*6H20(c) 
[Formation: Co(c) + S(c,«,) + 5 OjCg) + eHjCg) = CoS0,,*6H20(c)] 



T, K 


cal/mol'K 




kcal/mol 




Log Kf 


Cp" 


S" 


-(G°- H|,8)/T 


H - "298 


AHf° 


AGf 











00 


-13.525 


-630,143 


-630.143 


00 


100 


33.674 


26.822 


146.552 


-11.973 


-636,651 


-603,724 


1319.420 


200 


61.028 


58,923 


94.848 


-7.185 


-640,057 


-569,293 


622,086 


298.15 


84.340 


87.863 


87.863 





-641.330 


-534,221 


391.590 


300 


84.759 


88.386 


87.866 


.156 


-641.338 


-533,556 


388.690 


337 


92.978 


98.715 


88.489 


3.446 


-641.315 


-520.260 


337.393 


350 


95.794 


102.287 


88.936 


4.673 


-641.241 


-515,596 


321.948 


368.30 


99.630 


107,267 


89.724 


6.461 


-641.086 


-509,030 


302.055 


568.30 


99.630 


107.267 


89,724 


6.461 


-641.182 


-509,030 


302.055 


388.36 


103.834 


112.667 


90,769 


8.504 


-640.938 


-501,837 


282,406 


388.36 


103,834 


112.667 


90,769 


8.504 


-641,351 


-501,837 


282,406 


400 


106.274 


115.769 


91,451 


9.727 


-641.195 


-497,658 


271,904 


432.02 


112.631 


124.200 


93,567 


13,234 


-640.655 


-486.188 


245,949 


450 


116.200 


128.865 


94.885 


15,291 


-640.349 


-479.762 


233.001 


500 


125.572 


141.598 


98.924 


21,337 


-639,026 


-461.986 


201.931 


550 


134.389 


153.984 


103.368 


27,839 


-637.273 


-444.363 


176.571 



Phase changes; 



Sources: 



337 K CoS0^*6H20(c) dissociates to CoS0i,*H20(c) and saturated solution. 
368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol, 
388,36 K, melting point of S; AH° = 0.413 kcal/mol, 
432,02 K, second-order transformation of S; AH° = kcal/mol. 

Enthalpy of formation at 298 K is from Ko (25), Entropy at 298 K and heat capacities 
are from Rao (40), The transition temperature is from Broers (6), 



TABLE 31, - Thermodynamic properties of CoS0,,*7H20(c) 
[Formation: Co(c) + S(c,ll) + 5,5 02(g) + 7H2(g) = CoS0^'7H20(c) ] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G"- H|9e)/T 


fjO ijO 

M - M290 


AHf° 


AGf 











00 


-15.097 


-699.423 


-699.423 


00 


100 


37.564 


28.644 


162.704 


-13.406 


-706.857 


-669.637 


1463,471 


200 


69.109 


64.777 


104.832 


-8.011 


-710,647 


-630.730 


689.220 


298.15 


93.483 


97.048 


97.048 





-712,100 


-591.120 


433,297 


300 


93.924 


97.628 


97.051 


.173 


-712,110 


-590.369 


430.078 


317.78 


98.144 


103.156 


97,237 


1.881 


-712,154 


-583.151 


401.051 


350 


105.746 


112.996 


98,236 


5.166 


-712.060 


-570.078 


355.968 


368.30 


110.019 


118.494 


99,107 


7.140 


-711.911 


-562.658 


333.878 


368.30 


110.019 


118.494 


99,107 


7.140 


-712.007 


-562.658 


333.878 


388.36 


114.703 


124.452 


100,263 


9.394 


-711.764 


-554.529 


312.057 


388.36 


114.703 


124.452 


100,263 


9.394 


-712.177 


-554,529 


312.057 


400 


117.421 


127.880 


101,018 


10.745 


-712.016 


-549,806 


300.396 


432.02 


124.804 


137.204 


103,354 


14.624 


-711.443 


-536,842 


271.574 


450 


128.949 


142,377 


104.810 


16.905 


-711.104 


-529,579 


257,195 


500 


140.331 


156.554 


109.278 


23.638 


-709.628 


-509,483 


222,692 


550 


151.565 


170.457 


114,210 


30.936 


-707.616 


-489,562 


194,531 



Phase changes : 317,78 K CoS0,,'7H20(c) dissociates to CoS0,,*6H20(c) and saturated solution; 
AH° = 2,848 kcal/mol (heptahydrate), 
368,3 K, orthorhombic-monoclinic transformation of S; AH° = 0,096 kcal/mol. 
388,36 K, melting point of S; AH° = 0,413 kcal/mol, 
432,02 K, second-order transformation of S; Ah° = kcal/mol. 



Sources: Enthalpy of formation at 298 K is based on Ko (25^) and Brodale (5^). 
298.15 K is from Rao (40). Heat capacities are from Rao (40). 



The entropy at 



29 



TABLE 32. - Thermodynamic properties of NiSO^(c) 
[Formation: Ni(c) + S(c,£) + 2 OjCg) = NiSO,,(c)] 



T, K 


cal/mol'K 


kcal/mol 




Log Kf 


Cp" 


S" 


-(G°- H;,s)/T 




AHf 


AGf° 











oo 


-3.810 


-206.172 


-206.172 


00 


100 


9.020 


6.760 


40.960 


-3.420 


-207.455 


-199.375 


435.728 


200 


17.840 


15.990 


26.190 


-2.040 


-208.312 


-190.929 


208.635 


298.15 


23.330 


24.210 


24.210 





-208.710 


-182.294 


133.623 


300 


23.420 


24.350 


24.217 


.040 


-208.718 


-182.131 


132.681 


368.30 


26.213 


29.492 


24.718 


1.758 


-208.788 


-176.066 


104.477 


368.30 


26.213 


29.492 


24.718 


1.758 


-208.884 


-176.066 


104.477 


388.36 


27.034 


30.905 


25.001 


2.293 


-208.890 


-174.278 


98.074 


388.36 


27.034 


30.905 


25.001 


2.293 


-209.303 


-174.278 


98.074 


400 


27.510 


31.710 


25.185 


2.610 


-209.320 


-173.228 


94.646 


432.02 


28.323 


33.860 


25.749 


3.504 


-209.374 


-170.338 


86.169 


500 


30.050 


38.140 


27.140 


5.500 


-209.539 


-164.174 


71.760 


600 


31.910 


43.790 


29.457 


8.600 


-209.588 


-155.098 


56.494 


631 


32.363 


45.409 


30.201 


9.596 


-209.591 


-152.281 


52.743 


700 


33.370 


48.820 


31.863 


11.870 


-209.472 


-146.011 


45.586 


717.82 


33.584 


49.662 


32.294 


12.467 


-209.425 


-144.396 


43.963 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
631 K, Curie temperature of Ni. 
717.824 K, boiling point of S to equilibrium mixture. 

Sources: Enthalpy of formation is based on Adami (2^). Low-temperature heat capacities are from 
Stuve (44) and Weller (50). High-temperature enthalpy data are from Stuve (44). 
Entropy at 298 K is from Stuve (44). 



TABLE 33. - Thermodynamic properties of NiSOi,(c) 
[Formation: Ni(c) + 0.5 S2(g) + 2 02(g) = NiSO^(c)] 



T, K 


cal/mol*K 


kcal/mol 




Log Kf 


Cp" 


S" 


-(G-- HS9e)/T 


H°- H298 


AHf 


AGf 











oo 


-3.810 


-221.490 


-221.490 


00 


100 


9.020 


6.760 


40.960 


-3.420 


-222.976 


-212.865 


465.210 


200 


17.840 


15.990 


26.190 


-2.040 


-223.794 


-202.390 


221.159 


298.15 


23.330 


24.210 


24.210 





-224.065 


-191.807 


140.597 


300 


23.420 


24.350 


24.217 


.040 


-224.070 


-191.608 


139.585 


400 


27.510 


31.710 


25.185 


2.610 


-223.971 


-180.794 


98.780 


500 


30.050 


38.140 


27.140 


5.500 


-223.667 


-170.028 


74.318 


600 


31.910 


43.790 


29.457 


8.600 


-223.283 


-159.339 


58.039 


631 


32.363 


45.409 


30.201 


9.596 


-223.166 


-156.037 


54.043 


700 


33.370 


48.820 


31.863 


11.870 


-222.797 


-148.707 


46.428 


800 


34.570 


53.360 


34.2.35 


15.260 


-222.176 


-138.181 


37.749 


900 


35.560 


57.490 


36.634 


18.770 


-221.482 


-127.720 


31.014 


1000 


36.380 


61.280 


38.910 


22.370 


-220.741 


-117.343 


25.645 


1100 


37.030 


64.780 


41.107 


26.040 


-219.975 


-107.032 


21.265 


1200 


37.530 


68.020 


43.212 


29.770 


-219.188 


-96.795 


17.629 



Phase change ; 631 K, Curie temperature of Ni. 

Sources: Enthalpy of formation at 298 K is based on Adami (.2). Low-temperature heat capacities 
are from Stuve ( 44 ) and Weller (50). High-temperature enthalpy data are from Stuve 
(44). Entropy at 298 K is from Stuve (44). 



30 



TABLE 34. - Thermodynamic properties of NiS0i,*H20(c) 
[Formation: Ni(c) + S{c,l) + 2.5 OjCg) + HjCg) = NiSO^'MjOCc)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- H5,b)/T 


n - H29B 


AHf 


LGf 


298.15 


32.597 


32.700 


32.700 





-284.600 


-244.105 


178.932 


300 


32.763 


32.902 


32.702 


.060 


-284.608 


-243.854 


177.645 


350 


37.260 


38.290 


33.116 


1.811 


-284.681 


-237.054 


148.021 


368.30 


38.906 


40.231 


33.421 


2.508 


-284.663 


-234.564 


139.189 


368,30 


38.906 


40.231 


33.421 


2.508 


-284.759 


-234. 564 


139.189 


388.36 


40.710 


42.341 


33.828 


3.306 


-284.712 


-231.830 


130.461 


388.36 


40.710 


42.341 


33.828 


3.306 


-285.125 


-231.830 


130.461 


400 


41.757 


43.559 


34.094 


3.786 


-285.103 


-230.234 


125.792 


432.02 


44.636 


46.884 


34.917 


5.170 


-285.005 


-225.844 


114.249 


450 


46.253 


48.737 


35.433 


5.987 


-284.989 


-223.383 


108.488 


500 


50.750 


53.843 


37.019 


8.412 


-284.650 


-216.554 


94.654 


550 


55.246 


58.891 


38.778 


11.062 


-284.099 


-209.770 


83.354 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



Sources: Enthalpy of formation at 298 K is based on Goldberg (15). 
Mah (31). Heat capacities are estimates. 



Entropy at 298 K is from 



TABLE 35. - Thermodynamic properties of NiS0i,*4H20(c) 
[Formation: Ni(c) + S(c,A) + 4 02(g) + 4H2(g) = NiS0^•4H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G°- H|„)/T 


H"- H5,8 


AHf 


AGf 


298.15 


60.500 


61.000 


61.000 





-499.400 


-417.513 


306.042 


300 


60.767 


61.375 


61.002 


.112 


-499.414 


-417.005 


303.784 


350 


67.973 


71.283 


61.766 


3.331 


-499.587 


-403.252 


251.799 


368.30 


70.611 


74.814 


62.327 


4.599 


-499.574 


-398.215 


236.298 


368.30 


70.611 


74.814 


62.327 


4.599 


-499.670 


-398.215 


236.299 


388.36 


73.502 


78.635 


63.070 


6.045 


-499.610 


-392.689 


220.983 


388.36 


73.502 


78.635 


63.070 


6.045 


-500.023 


-392.689 


220.983 


400 


75.180 


80.830 


63.555 


6.910 


-499.984 


-389.473 


212.796 


432.02 


79.795 


86.795 


65.058 


9.391 


-499.807 


-380.634 


192.552 


450 


82.387 


90.102 


65.993 


10.849 


-499.725 


-375.677 


182.451 


500 


89.593 


99.155 


68.859 


15.148 


-499.113 


-361.923 


158.194 


550 


96.800 


108.032 


72.017 


19.808 


-498.163 


-348.248 


138.379 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; Ah° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah° = kcal/mol. 



Sources: Enthalpy of formation at 298 K — see discussion in text, 
at 298 K are estimates. 



Heat capacities and entropy 



31 



TABLE 36. - Thermodynamic properties of NiS0i,*6H20(a,c) 
[Formation: Ni(c) + S(c,i) + 5 OjCg) + 6H2(g) = NiS0H*6H20(a,c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(C- H|98)/T 


H"- H|,a 


AHf° 


AGf° 











00 


-12.391 


-629.014 


-629.014 


00 


100 


29.980 


23.841 


134.231 


-11.039 


-635.719 


-602.500 


1316.745 


200 


56.680 


53.128 


86.428 


-6.660 


-639.529 


-567.626 


620.265 


298.15 


78.361 


79.935 


79.935 





-641.340 


-531.879 


389.873 


300 


78.730 


80.421 


79.938 


.145 


-641.360 


-531.200 


386.974 


350 


88.180 


93.280 


80.931 


4.322 


-641.620 


-512.814 


320.211 


368.30 


91.254 


97.852 


81.660 


5.964 


-641.618 


-506.079 


300.304 


368.30 


91.254 


97.852 


81.660 


5.964 


-641.714 


-506.079 


300.304 


388.36 


94.624 


102.792 


82.622 


7.833 


-641.653 


-498.691 


280.635 


388.36 


94.624 


102.792 


82.622 


7.833 


-642.066 


-498.691 


280.635 


400 


96.579 


105.615 


83.250 


8.946 


-642.025 


-494.395 


270.121 


432.02 


101.285 


113.241 


85.191 


12.118 


-641.836 


-482.584 


244.126 


450 


103.928 


117.425 


86.396 


13.963 


-641.749 


-475.959 


231.154 


500 


110.227 


128.710 


90.068 


19.321 


-641.146 


-457.567 


200 


550 


115.476 


139.470 


94.074 


24.968 


-640.283 


-439.250 


174.540 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 

Sources: Enthalpy of formation is based on Goldberg (15). Low-temperature heat capacities and 
entropies are from Stout (43). Heat capacities above 300 K are estimates. 



TABLE 37. - Thermodynamic properties of NiS0i,*7H20(c) 
[Formation: Ni(c) + S(c,il) + 5.5 02(g) + 7H2(g) = NiS0„*7H20(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp° 


S° 


-(G°- HU,)/1 


IjO ijO 

H - H298 


AHf° 


AGf° 











00 


-14.085 


-697.707 


-697.707 


00 


100 


34.700 


26.549 


152.079 


-12.553 


-705.296 


-667.872 


1459.615 


200 


64.800 


60.327 


97.867 


-7.508 


-709.432 


-628.644 


686.941 


298.15 


87.142 


90.570 


90.570 





-711.400 


-588.500 


431.377 


300 


87.503 


91.110 


90.570 


.162 


-711.423 


-587.737 


428.161 


304 


88.277 


92.274 


90.587 


.513 


-711.466 


-586.088 


421.342 


350 


96.425 


105.290 


91.670 


4.767 


-711.777 


-567.089 


354.102 


368.30 


99.098 


110.272 


92.472 


6.556 


-711.820 


-559.523 


332.017 


368.30 


99.098 


110.272 


92.472 


6.556 


-711.916 


-559.523 


332.017 


388.36 


102.028 


115.622 


93.530 


8.580 


-711.912 


-551.222 


310.196 


388.36 


102.028 


115.622 


93.530 


8.580 


-712.325 


-551.222 


310.196 


400 


103.728 


118.660 


94.218 


9.777 


-712.323 


-546.393 


298.532 


432.02 


107.368 


126.8 


96.333 


13.163 


-712.258 


-533.113 


269.687 


450 


109.412 


131.222 


97.640 


15.112 


-712.260 


-525.659 


255.292 


500 


113.477 


142.974 


101.592 


20.691 


-711.969 


-504.939 


220.706 


550 


115.923 


153.917 


105.857 


26.433 


-711.548 


-484.257 


192.423 



Phase changes ; 304 K NiS0^•7H20(c) dissociates to NiS0^•6H20(c) and saturated solution. 

368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 

388.36 K, melting point of S; AH" = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH° = kcal/mol. 



Sources; Enthalpy of formation at 298 K is based on Goldberg (15). 
and transition temperature are from Stout (43). 



Heat capacities, entropies, 



32 



TABLE 38. - Thermodynamic properties of CuSOi,(c) 
[Formation: Cu(c) + S(c,il) + 2 OjCg) = CuSO^(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- Hl,8)/T 


H""- H2,e 


AHf 


AGf 











00 


-4.032 


-181.932 


-181.932 


00 


100 


10.454 


7.865 


43.425 


-3.556 


-183.168 


-175.136 


382.756 


200 


18.419 


17.786 


28.176 


-2.078 


-183.956 


-166.762 


182.227 


298.15 


23.632 


26.173 


26.173 





-184.300 


-158.235 


115.988 


300 


23.710 


26.319 


26.172 


.044 


-184.303 


-158.072 


115.154 


368.30 


26.353 


31.491 


26.685 


1.770 


-184.330 


-152.095 


90.252 


368.30 


26.353 


31.491 


26.685 


1.770 


-184.426 


-152.095 


90. 252 


388.36 


27.130 


32.910 


26.971 


2.307 


-184.416 


-150.334 


84.599 


388.36 


27.130 


32.910 


26.971 


2.307 


-184.829 


-150.334 


84. 599 


400 


27.580 


33.718 


27.155 


2.625 


-184.836 


-149.300 


81.573 


432.02 


28.448 


35.875 


27.723 


3.522 


-184.859 


-146.455 


74.088 


500 


30.290 


40.180 


29.128 


5.526 


-184.946 


-140.401 


61.368 


600 


32.300 


45.889 


31.456 


8.660 


-184.805 


-131.500 


47.898 


700 


33.890 


50.991 


33.888 


11.972 


-184.488 


-122.639 


38.289 


717.82 


34.136 


51.846 


34.323 


12.578 


-184.416 


-121.065 


36.859 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah" = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 



Sources: The enthalpy of formation at 298 K and entropy at 298 K are from CODATA (8). 
capacities are from King (23). 



Heat 



TABLE 39. - Thermodynamic properties of CuSOi,(c) 
[Formation: Cu(c) + 0.5S2(g) + 2 OjCg) = Cu50^(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- HS98)/T 


H - H298 


AHf 


AGf 











00 


-4.032 


-197.250 


-197.250 


00 


100 


10.454 


7.865 


43.425 


-3.556 


-198.689 


-188.626 


412.237 


200 


18.419 


17.786 


28.176 


-2.078 


-199.439 


-178.224 


194.751 


298.15 


23.632 


26.173 


26.173 





-199.655 


-167.749 


122.962 


300 


23.710 


26.319 


26.172 


.044 


-199.655 


-167.550 


122.058 


400 


27.580 


33.718 


27.155 


2.625 


-199.487 


-156.866 


85.706 


500 


30.290 


40.180 


29.128 


5.526 


-199.074 


-146.254 


63.927 


600 


32.300 


45.889 


31.456 


8.660 


-198.499 


-135.741 


49.443 


700 


33.890 


50.991 


33.888 


11.972 


-197.813 


-125.334 


39.131 


800 


35.270 


55.609 


36.320 


15.431 


-197.036 


-115.034 


31.426 


900 


36.530 


59.836 


38.700 


19.022 


-196.176 


-104.834 


25.457 


1000 


37.700 


63.747 


41.013 


22.734 


-195.238 


-94.736 


20.704 


1100 


38.730 


67.390 


43.246 


26.558 


-194.232 


-84.731 


16.834 



Sources: The enthalpy of formation at 298 K and entropy at 298 K are from CODATA (B) . 
capacities are from King (23). 



The heat 



33 



TABLE 40. - Thermodynamic properties of CuS0i,*H20(c) 
[Formation: Cu(c) + S(c,A) + 2.5 OjCg) + HjCg) = CuSO^'HjOCc)] 



T, K 


cal/mol»K 


kcal/mol 


Log Kf 


Cp' 


S° 


-(C- H5,8)/T 


H°- H,%, 


AHf 


AGf 


298.15 


32.000 


34.900 


34.900 





-259.520 


-219.447 


160.857 


300 


32.180 


35.099 


34.902 


.059 


-259.527 


-219.199 


159.684 


350 


36.678 


40.397 


35.308 


1.781 


-259.606 


-212.468 


132.669 


368.30 


38.324 


42.308 


35.609 


2.467 


-259.587 


-210.003 


124.615 


368.30 


38.324 


42.308 


35.609 


2.467 


-259.683 


-210.003 


124.615 


388.36 


40.129 


44.387 


36.009 


3.254 


-259.634 


-207.298 


116.656 


388.36 


40.129 


44.387 


36.009 


3.254 


-260.047 


-207.298 


116.656 


400 


41.176 


45.588 


36.271 


3.727 


-260.022 


-205.718 


112.397 


432.02 


44.057 


48.869 


37.084 


5.091 


-259.918 


-201.375 


101.870 


450 


45.674 


50.698 


37.591 


5.898 


-259.897 


-198.940 


96.617 


500 


50.172 


55.743 


39.153 


8.295 


-259.530 


-192.183 


84.002 


550 


54.670 


60.736 


40.889 


10.916 


-258.942 


-185.474 


73.699 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 

Sources: The enthalpy of formation at 298 K, entropy at 298 K, and heat capacity at 298 K are 
from Wagman (48). The high-temperature heat capacities are estimates. 



TABLE 41. - Thermodynamic properties of CuS0^'3H20(c) 
[Formation: Cu(c) + S(c,A) + 3.5 OaCg) + 3H2(g) = CuS0^'3H20(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S° 


-(G°- H|98)/T 


H"- HUs 


AHf° 


AGf 


298.15 


49.000 


52.900 


52.900 





-402.560 


-334.634 


245.290 


300 


49.244 


53.204 


52.901 


.091 


-402.574 


-334.212 


243.470 


350 


55.843 


61.290 


53.524 


2.718 


-402.793 


-322.797 


201.561 


368.30 


58.259 


64.198 


53.983 


3.762 


-402.801 


-318.614 


189.064 


368.30 


58.259 


64.198 


53.983 


3.762 


-402.897 


-318.614 


189.064 


388.36 


60.907 


67.357 


54.592 


4.957 


-402.862 


-314.024 


176.715 


388.36 


60.907 


67.357 


54.592 


4.957 


-403.275 


-314.024 


176.715 


400 


62.443 


69.178 


54.991 


5.675 


-403.251 


-311.349 


170.111 


432.02 


66.669 


74.147 


56.227 


7.742 


-403.122 


-303.997 


153.784 


450 


69.042 


76.914 


56.998 


8.962 


-403.071 


-299.874 


145.637 


500 


75.641 


84.530 


59.372 


12.579 


-402.552 


-288.432 


126.072 


550 


82.240 


92.048 


62.001 


16.526 


-401.712 


-277.056 


110.091 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 

Sources: The enthalpy of formation at 298 K, entropy at 298 K, and heat capacity at 298 K are 
from Wagman (48). High-temperature heat capacities are estimates. 



34 



TABLE 42. - Thermodynamic properties of CuS0^*5H20(c) 
[Formation: Cu(c) + S(c,l) + 4.5 OjCg) + 5H2(g) = CuSOh'SHjOCc)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S° 


-(C- H59e)/T 


H'- H2,a 


AHf 


AGf° 


298.15 


67.000 


71.800 


71.800 





-544.870 


-449. 360 


329.385 


300 


67.360 


72.216 


71.803 


.124 


-544.890 


-448.767 


326.923 


350 


76.354 


83.275 


72.655 


3.717 


-545.188 


-432.717 


270.197 


368.30 


79.646 


87.250 


73.282 


5.144 


-545.197 


-426.836 


253.282 


368.30 


79.646 


87.250 


73.282 


5.144 


-545.293 


-426.836 


253.282 


388.36 


83.254 


91.567 


74.113 


6.779 


-545.242 


-420.383 


236.568 


388.36 


83.254 


91 . 567 


74.113 


6.779 


-545.655 


-420.383 


236.568 


400 


85.348 


94.057 


74.657 


7.760 


-545.613 


-416.629 


227.633 


432.02 


91 . 1 08 


100.848 


76.347 


10.585 


-545.405 


-406.312 


205.542 


450 


94.342 


104.629 


77.402 


12.252 


-545.290 


-400.526 


194.520 


500 


103.336 


115.035 


80.647 


17.194 


-544.513 


-384.479 


168.053 


550 


112.330 


125.305 


84.240 


22.586 


-543.302 


-368.529 


146.438 



Phase changes ; 368.3 K, orthorhombic-monoclinic transformation of S; AH" = 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 



Sources: The enthalpy of formation at 298 K is based on Larson (29). 
capacity at 298 K are from Wagman (48). 



The entropy and heat 



TABLE 43. - Thermodynamic properties of Cu2S0^(c) 
[Formation: 2Cu(c) + S(c,ll) + 2 02(g) = Cu2S0„(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(C- H|98)/T 


H - H298 


AHf° 


AGf 


298.15 


31.000 


43.600 


43.600 





-179.600 


-156.368 


114.620 


300 


31.068 


43.792 


43.602 


.057 


-179.601 


-156.224 


113.808 


368.30 


33.489 


50.411 


44.262 


2.265 


-179.550 


-150.905 


89.546 


368.30 


53.489 


50.411 


44.262 


2.265 


-179.646 


-150.905 


89.546 


388.36 


34.200 


52.206 


44.627 


2.944 


-179.614 


-149.339 


84.040 


388.36 


34.200 


52.206 


44.627 


2.944 


-180.027 


-149.339 


84.040 


400 


34.613 


53.222 


44.862 


3.344 


-180.022 


-148.420 


81.092 


432.02 


35.657 


55.928 


45.583 


4.469 


-180.011 


-145.891 


73.802 


500 


37.872 


61.301 


47.361 


6.970 


-180.019 


-140.518 


61.420 


600 


40.846 


68.473 


50.291 


10.909 


-179.699 


-132.640 


48.314 


700 


43.535 


74.975 


53.361 


15.130 


-179.112 


-124.840 


38.976 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of 5; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH" = kcal/mol. 



Sources: The enthalpy of formation at 298 K is from Wagman (48), 
Nagamori (35). The heat capacities are estimates. 



The entropy at 298 K is from 



35 



TABLE 44. - Thermodynamic properties of CuO*CuSOh(c) 
[Formation: 2Cu(c) + S(c,Jl) + 2.5 OzCg) = CuO'CuSO^ (c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(C- H|98)/T 


H°- Hlse 


AHf 


AGf° 














-5.909 


-216.376 


-216.376 





100 


16.148 


13.806 


65.066 


-5.126 


-217.812 


-208.065 


454.719 


200 


26.484 


28.410 


43.205 


-2.959 


-218.740 


-197.915 


216.268 


298.15 


33.450 


40.358 


40.358 





-219.100 


-187.596 


137.510 


300 


33.570 


40.565 


40.358 


.062 


-219.103 


-187.400 


136.519 


368.30 


36.659 


47.790 


41.078 


2.472 


-219.091 


-180.180 


106.918 


368.30 


36.659 


47.790 


41.078 


2.472 


-219.187 


-180.181 


106.918 


388.36 


37.566 


49.759 


41.476 


3.217 


-219.161 


-178.056 


100.200 


388.36 


37.566 


49.759 


41.476 


3.217 


-219.574 


-178.056 


100.200 


400 


38.092 


50.876 


41.734 


3.657 


-219.571 


-176.812 


96.604 


432.02 


39.144 


53.850 


42.523 


4.894 


-219.564 


-173.390 


87.713 


500 


41.376 


59.750 


44.470 


7.640 


-219.576 


-166.119 


72.610 


600 


43.701 


67.511 


47.678 


11.900 


-219.313 


-155.448 


56.621 


700 


45.332 


74.378 


51.011 


16.357 


-218.879 


-144.835 


45.219 


717.82 


45.547 


75.520 


51.605 


17.167 


-218.788 


-142.951 


43.523 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah° = kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 

Source: All data are from King (23). 



TABLE 45. - Thermodynamic properties of CuO*CuSOi,(c) 
[Formation: 2Cu(c) + 0.5S2(g) + 2.5 02(g) = CuO»CuSO^(c)] 



T, K 


cal/mol'K 


kcal/mol 


Log Kf 


Cp" 


S" 


-(G°- \^Ua)/^ 


11° u° 
H - H298 


AHf° 


AGf 














-5.909 


-231.693 


-231.693 





100 


16.148 


13.806 


65.066 


-5.126 


-233.332 


-221.554 


484.201 


200 


26.484 


28.410 


43.205 


-2.959 


-234.222 


-209.376 


228.793 


298.15 


33.450 


40.358 


40.358 





-234.455 


-197.110 


144.484 


300 


33.570 


40.565 


40.358 


.062 


-234.455 


-196.877 


143.423 


400 


38.092 


50.876 


41.734 


3.657 


-234.222 


-184.378 


100.738 


500 


41.376 


59.750 


44.470 


7.640 


-233.704 


-171.973 


75.168 


600 


43.701 


67.511 


47.678 


1 1 . 900 


-233.007 


-159.689 


58.166 


700 


45.332 


74.378 


51.011 


16.357 


-232.204 


-147.530 


46.060 


800 


46.539 


80.513 


54.322 


20.953 


-231.340 


-135.495 


37.015 


900 


47.587 


86.055 


57.545 


25.659 


-230.435 


-123.568 


30.006 


1000 


48.744 


91.127 


60.653 


30.474 


-229.483 


-111.745 


24.421 


1100 


50.278 


95.840 


63.640 


35.420 


-228.466 


-100.017 


19.871 


1200 


52.455 


100.303 


66.511 


40.551 


-227.336 


-88.387 


16.097 



Source: All data are from King (23). 



36 



TABLE 46. - Thermodynamic properties of ZnSOi,(c) 
[Formation: Zn(c,il) + S(c,Jl) + 2 OjCg) = ZnSO^(c)] 



T, K 


cal/mol*K 


kcal/mol 


r ■ — 

Log Kf 


Cp" 


S" 


-(C- H29e)/T 


H"- H2,8 


AHf 


AGf 











00 


-4.120 


-231.823 


-231.823 


00 


100 


11.373 


7.548 


43.868 


-3.632 


-233.125 


-224.907 


491.527 


200 


18.655 


17.979 


28.429 


-2.090 


-233.902 


-216.360 


236.425 


298.15 


23.680 


26.430 


26.430 





-234.260 


-207.668 


152.223 


300 


23.746 


26.577 


26.430 


.044 


-234.263 


-207.502 


151.163 


368.30 


25.885 


31.681 


26.938 


1.747 


-234.330 


-201.400 


119.509 


368.30 


25.885 


31.681 


26.938 


1.747 


-234.426 


-201.400 


119.510 


388.36 


26.513 


33.071 


27.220 


2.272 


-234.431 


-199.600 


112.324 


388.36 


26.513 


33.071 


27. 220 


2.272 


-234.844 


-199.600 


112.324 


400 


26.878 


33.859 


27.402 


2.583 


-234.862 


-198.544 


108.478 


432.02 


27.719 


35.961 


27.959 


3.457 


-234.917 


-195.635 


98.966 


500 


29.506 


40.144 


29.336 


5.404 


-235.080 


-189.437 


82.802 


600 


31.945 


45.741 


31.611 


8.478 


-235.039 


-180.307 


65.676 


692.73 


34.124 


50.486 


33.825 


11.541 


-234.805 


-171.866 


54.222 


692.73 


34.124 


50.486 


33.825 


11.541 


-236.555 


-171.866 


54.222 


700 


34.295 


50.843 


34.000 


11.790 


-236.533 


-171.187 


53.446 


717.82 


34.705 


51.710 


34.429 


12.405 


-236.470 


-169.524 


51.613 



Phase changes: 



Sources: 



368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 

388.36 K, melting point of S; AH° = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH° = kcal/mol. 

692.73 K, melting point of Zn; AH" = 1.750 kcal/mol. 

717.824 K, boiling point of S to equilibrium mixture. 

Enthalpy of formation at 298 K is based on Adami (2). Heat capacities of a-ZnSOj, are 
from Weller ( 50 ) and Voskresenskaya (46). Enthalpy and entropy values are taken from 
JANAF (12). 



37 



TABLE 47. - Thermodynamic properties of ZnSOi,(c) 







[Formation: Zn(c,A,g) + 


0.5S2(g) + 


Z OjCg) = ZnS0^(c)] 




T, K 


cal/mol*K ! 


kcal/mol ] 


Log Kf 


Cp- 


S° 


-(C- H|58)/T 


H°- Hiss 


AHf° 


AGf° 











OS 


-4.120 


-247.141 


-247.141 


00 


100 


11.373 


7.548 


43.868 


-3.632 


-248.645 


-238.397 


521.009 


200 


18.655 


17.979 


28.429 


-2.090 


-249.384 


-227.822 


248.949 


298.15 


23.680 


26.430 


26.430 





-249.615 


-217.181 


159.196 


300 


23.746 


26.577 


26.430 


.044 


-249.615 


-216.979 


158.067 


aoo 


26.878 


33.859 


27.402 


2.583 


-249.513 


-206.110 


112.612 


500 


29.506 


40.144 


29.336 


5.404 


-249.207 


-195.290 


85.360 


600 


31.945 


45.741 


31.611 


8.478 


-248.734 


-184.548 


67.221 


692.73 


34.124 


50.486 


33.825 


11.541 


-248.156 


-174.672 


55.107 


692.73 


34.124 


50.486 


33.825 


11.541 


-249.906 


-174.672 


55.107 


700 


34.295 


50.843 


34.000 


11.790 


-249.858 


-173.882 


54. 288 


800 


36.597 


55.573 


36.404 


15.335 


-249.094 


-163.080 


44.551 


900 


38.871 


60.015 


38.783 


19.109 


-248.139 


-152.383 


37.003 


1000 


41.128 


64.227 


41.118 


23.109 


-246.986 


-141.804 


30.991 


1015 


41.466 


64.842 


41.285 


23.910 


-246.615 


-140.046 


30.154 


1015 


34.700 


69.640 


41.285 


28.780 


-241.745 


-140.046 


30.154 


1100 


34.700 


72.431 


43.586 


31.729 


-241.241 


-131.549 


26.136 


1180 


34.700 


74.867 


45.625 


34.505 


-240.781 


-123.584 


22.889 


1180 


34.700 


74.867 


45.625 


34. 505 


-268.346 


-123.584 


22.889 


1200 


34.700 


75.450 


46.117 


35.199 


-268.184 


-121.134 


22.061 



Phase changes ; 692.73 K, melting point of Zn; AH° = 1.750 kcal/mol. 

1015 K, a-B transition point for ZnSO^Cc); Ah° = 4.87 kcal/mol. 
1180 K, boiling point of Zn; Ah° = 27.565 kcal/mol. 

Sources: Enthalpy of formation at 298 K is based on Adami (2). Heat capacities of a-ZnSO^ are 
from Weller (50) and Voskresenskaya (46). Heat capacities of B-ZnSOi, and AH for the 
ot-3 transition are from Hosmer (16). Enthalpy and entropy values are taken from JANAF 
(12). ~ 



TABLE 48. - Thermodynamic properties of ZnS0i,*H20(c) 
[Formation: Zn(c) + S(c,ll) + 2.5 02(g) + H2(g) = ZnS0^*H20(c)] 



T 1^ 




cal/mol*K 






kcal/mol 




1 nn Vf 


1 , K 


Cp° 


S° 


-(G°- H53e)/T 


H - H298 


AHf° 


AGf 




298.15 


36.153 


33.100 


33.100 





-311.850 


-270.637 


198.379 


300 


36.319 


33.324 


33.101 


.067 


-311.850 


-270.380 


196.969 


350 


40.819 


39.261 


33.561 


1.995 


-311.734 


-263.476 


164.520 


368.30 


42.466 


41.383 


33.897 


2.757 


-311.643 


-260.955 


154.849 


368.30 


42.466 


41.383 


33.897 


2.757 


-311.740 


-260.955 


154.849 


388.36 


44.272 


43.682 


34.341 


3.628 


-311.612 


-258.190 


145.295 


388.36 


44.272 


43.682 


34.341 


3.628 


-312.025 


-258.190 


145.295 


400 


45.320 


45.005 


34.632 


4.149 


-311.955 


-256.578 


140.186 


432.02 


48.202 


48.605 


35.536 


5.646 


-311.726 


-252.155 


127.558 


450 


49.820 


50.603 


36.099 


6.527 


-311.634 


-249.678 


121.258 


500 


54.320 


56.085 


37.823 


9.131 


-311.076 


-242.820 


106.135 


550 


58.820 


61.473 


39.729 


11.959 


-310.299 


-236.030 


93.788 


Phase ch 


anges: 368 


. 3 K, orthorhombic-monoclinic transformation of S; 


AH° = 0.096 kcal/mol. 



388.36 K, melting point of S; AH° = 0.413 kcal/mol. 

432.02 K, second-order transformation of S; AH° = kcal/mol. 

Sources: Enthalpy of formation is based on Wagman (47). Entropy at 298 K is from Wagman (47). 
Heat capacity at 298 K is from Kelley (21 ), and high-temperature heat capacities are 
estimates. 



38 



TABLE 49. - Thermodynamic properties of ZnS0H*6H20(c) 
[Formation: Zn(c) + S(c,Jl) + 5 OjCg) + 6H2(g) = ZnS0^•6H20(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cpo 


S' 


-(C- H59e)/T 


U|0 u** 


AHf° 


AGf° 


298.15 


84.994 


86.900 


86.900 





-663.900 


-555.678 


407.318 


300 


85.456 


87.427 


86.900 


.158 


-663.906 


-555.006 


404.316 


333.40 


93.988 


96.887 


87.430 


3.153 


-663.862 


-542.882 


355.865 


350 


98.362 


101.559 


87.988 


4.750 


-663.739 


-536.860 


335.226 


368.30 


103.380 


106.700 


88.791 


6.596 


-663.526 


-530.231 


314.636 


368.30 


103.380 


106.700 


88.791 


6.596 


-663.622 


-530.231 


314.636 


388.36 


108.880 


112.317 


89.861 


8.721 


-663.296 


-522.973 


294.300 


388.36 


108.880 


112.317 


89.861 


8.721 


-663.709 


-522.973 


294.300 


400 


112.072 


115.580 


90.563 


10.007 


-663.489 


-518.759 


283.433 


432.02 


121.367 


124.555 


92.749 


13.741 


-662.719 


-507.201 


256.579 


450 


126.586 


129.610 


94.121 


15.970 


-662.238 


-500.740 


243.189 


500 


141.904 


143.733 


98.375 


22.679 


-660.243 


-482.895 


211.071 


550 


158.026 


158.008 


103.146 


30.174 


-657.484 


-465.287 


184.886 



Phase chanqes: 



Sources: 



ZnS0i,*6H20(c) dissociates to ZnS0i,*H20(c) and saturated solution at 333.4 K. 
368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; Ah° = kcal/mol. 

The enthalpy of formation at 298 K is based on Larson (29). The entropy and heat 
capacity at 298 K are from Barieau (4). The high-temperature heat capacity values are 
obtained by extrapolating the low-temperature values of Barieau (4^) . 



TABLE 50. - Thermodynamic properties of ZnS0i,*7H20(c) 
[Formation: Zn(c) + S(c,)l) + 5.5 02(g) + 7H2(g) = ZnS0H'7H20(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(G-- H^,g)/T 


mo ijO 

M - M298 


AHf 


AGf° 











00 


-14.592 


-722.154 


-722.154 


OS 


100 


36.630 


26.991 


156.231 


-12.924 


-729.724 


-692.129 


1512.627 


200 


66.139 


61.789 


100.464 


-7.735 


-733.798 


-652.747 


713.279 


298.15 


91.144 


92.900 


92.900 





-735.550 


-612.507 


448.974 


300 


91.620 


93.465 


92.902 


.169 


-735.564 


-611.743 


445.649 


311.27 


94. 590 


96.898 


92.982 


1.219 


-735.625 


-607.090 


426.246 


350 


103.820 


108.512 


94.063 


5.057 


-735.624 


-591.093 


369.090 


368.30 


108.143 


113.913 


94.917 


6.996 


-735.509 


-583.539 


346.268 


368.30 


108.143 


113.913 


94.917 


6.996 


-735.605 


-583.539 


346.268 


388.36 


112.881 


119.776 


96.048 


9.215 


-735.398 


-575.260 


323.724 


388.36 


112.881 


119.776 


96.048 


9.215 


-735.811 


-575.260 


323.724 


400 


115.631 


123.150 


96.788 


10.545 


-735.669 


-570.450 


311.676 


432.02 


122.962 


132.336 


99.083 


14.366 


-735.152 


-557.244 


281.894 


450 


127.078 


137.434 


100.514 


16.614 


-734.843 


-549.847 


267.039 


500 


138.163 


151.400 


104.906 


23.247 


-733.458 


-529.360 


231.380 


550 


148.885 


165.074 


109.756 


30.425 


-731.553 


-509.038 


202.270 



Phase changes ; 311.27 K, ZnS0i,*7H20(c) dissociates to ZnS0^*6H20 and saturated solution with AH 
of dissociation = 4.017 kcal/mol hydrate. 
368.3 K, orthorhombic-monoclinic transformation of S; Ah° r 0.096 kcal/mol. 
388.36 K, melting point of S; AH° = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 

Sources: The enthalpy of formation at 298 K is based on Larson (29). The entropy at 298 K and 
heat capacities are from Barieau (4). The AH of dissociation is from Barieau (4). 



39 



TABLE 51. - Thermodynamic properties of Zn0'2ZnS0i,(c) 
[Formation: 3Zn(c,A) + 2S(c,i) + 4.5 OzCg) = ZnO»2ZnSO„(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S" 


-(C- Hl98)/T 


H - M298 


AHf° 


AGf° 


298.15 


56.686 


68.190 


68.190 





-550.310 


-491.424 


360.219 


300 


56.939 


68.541 


68.191 


.105 


-550.317 


-491.056 


357.730 


368.30 


63.332 


81.017 


69.425 


4.269 


-550.352 


-477.553 


283.377 


368.30 


63.332 


81.017 


69.425 


4.269 


-550.544 


-477.553 


283.377 


388.36 


65.209 


84.427 


70.114 


5.559 


-550.514 


-473.577 


266.502 


388.36 


65.209 


84.427 


70.114 


5.559 


-551.340 


-473.578 


266.503 


400 


66.299 


86.369 


70.559 


6.324 


-551.346 


-471.247 


257.474 


432.02 


67.919 


91.537 


71.925 


8.473 


-551.373 


-464.835 


235.147 


500 


71.359 


101.753 


75.297 


13.228 


-551.526 


-451.197 


197.215 


600 


74.727 


115.077 


80.842 


20.541 


-551.323 


-431.143 


157.042 


692.73 


77.108 


125.991 


86.169 


27.586 


-550.943 


-412.604 


130.171 


692.73 


77.108 


125.991 


86.169 


27.586 


-556.193 


-412.603 


130.171 


700 


77.295 


126.797 


86.587 


28.147 


-556.168 


-411.096 


128.348 


717.82 


77.677 


128.745 


87.609 


29.528 


-556.095 


-407.403 


124.038 



Phase changes : 368.3 K, orthorhombic-monoclinic transformation of S; AH° = 0.096 kcal/mol. 
388.36 K, melting point of S; AH" = 0.413 kcal/mol. 
432.02 K, second-order transformation of S; AH° = kcal/mol. 
692.73 K, melting point of Zn; AH° = 1.750 kcal/mol. 
717.824 K, boiling point of S to equilibrium mixture. 



Sources: The enthalpy at 298.15 K is from Ko (25). 
at 298.15 K are from Hosmer (16). 



High-temperature enthalpies and the entropy 



TABLE 52. - Thermodynamic properties of Zn0*2ZnS0H(c) 
[Formation: 3Zn(c,il,g) + S2(g) + 4.5 02(g) = Zn0*2ZnS0^(c)] 



T, K 


cal/mol*K 


kcal/mol 


Log Kf 


Cp° 


S° 


-(C- HS98)/T 


H - H29e 


AHf 


AGf 


298.15 


56.686 


68.190 


68.190 





-581.020 


-510.451 


374.166 


300 


56.939 


68.541 


68.191 


.105 


-581.021 


-510.011 


371.538 


400 


66.299 


86.369 


70.559 


6.324 


-580.648 


-486.378 


265.741 


500 


71.359 


101.753 


75.297 


13.228 


-579.781 


-462.903 


202.332 


600 


74.727 


115.077 


80.842 


20.541 


-578.711 


-439.625 


160.131 


692.73 


77.108 


125.991 


86.169 


27.586 


-577.643 


-418.216 


131.941 


692.73 


77.108 


125.991 


86.169 


27.586 


-582.893 


-418.214 


131.941 


700 


77.295 


126.797 


86.587 


28.147 


-582.818 


-416.486 


130.031 


800 


79.438 


137.261 


92.279 


35.986 


-581.690 


-392.802 


107.307 


900 


81.333 


146.729 


97.811 


44.026 


-580.443 


-369.266 


89.669 


1000 


83.074 


155.389 


103.141 


52.248 


-579.080 


-345.874 


75.590 


1100 


84.714 


163.385 


108.260 


60.638 


-577.610 


-322.622 


64.098 


1180 


85.972 


169.376 


112.202 


67.465 


-576.354 


-304.112 


56.324 


1180 


85.972 


169.376 


112.202 


67.465 


-659.049 


-304.112 


56.324 


1200 


86.286 


170.824 


113.167 


69.188 


-658.574 


-298.104 


54.292 



Phase changes : 692.73 K, melting point of Zn; Ah° = 1.750 kcal/mol. 

1015 K, a-B transition point for ZnSO^(c); AH° = 4.87 kcal/mol. 
1180 K, boiling point of Zn; AH" = 27.565 kcal/mol. 



Sources: The enthalpy at 298.15 K is from Ko (25). 
at 298.15 K are from Hosmer (16). 



High-temperature enthalpies and the entropy 



40 



TABLE 53. - Thermodynamic ciata for the reaction 
1/3Cr2(S0j3(c) = 1/3Cr20j(c) + SO3 (g) 



TABLE 56. - Thermodynamic data for the reaction 
CoSO^(c) = CoO(c) + SOj(g) 



T, K 


AH% 
kcal 


AG% 
kcal 


1 

Log K 


298.15 


49.872 


35.801 


-26.242 


300 


49.870 


35.713 


-26.016 


305 


49.868 


35.477 


-25.421 


400 


49.636 


31.025 


-16.951 


500 


49.256 


26.412 


-11.545 


600 


48.754 


21.891 


-7.974 


700 


48.145 


17.461 


-5.452 


800 


47.459 


13.122 


-3.585 


900 


46.737 


8.877 


-2.156 



Phase change : 305 K, second-order transition 

point of Cr203; AH° = kcal/mol. 



TABLE 54. - Thermodynamic data for the reaction 
FeSO^(c) = FeO(c) + SOjCg) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 


298.15 


63.220 


49.220 


-36.079 


300 


63.219 


49.133 


-35.793 


400 


63.130 


44.448 


-24.285 


500 


62.892 


39.802 


-17.397 


600 


62.552 


35.215 


-12.827 


700 


62.144 


30.689 


-9.581 


800 


61.695 


26.226 


-7.165 


900 


61.226 


21.820 


-5.299 


1000 


60.748 


17.468 


-3.818 


1100 


60.262 


13.162 


-2.615 


1200 


59.769 


8.902 


-1.621 


1300 


59.270 


4.686 


- .788 


1400 


58.762 


.504 


- .079 


1500 


58.245 


-3.641 


.530 


1600 


57.718 


-7.748 


1.058 



TABLE 55. - Thermodynamic data for the reaction 
1/3Fe2(S0^)3(c) = 1/3Fe203(c) + S03(g) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 


298.15 


45.439 


31.786 


-23.300 


300 


45.437 


31.702 


-23.094 


400 


45.268 


27.146 


-14.832 


500 


45.042 


22.641 


-9.896 


600 


44.760 


18.186 


-6.624 


700 


44.419 


13.784 


-4.303 


800 


44.022 


9.433 


-2.577 


800 


43.854 


9.433 


-2.577 


900 


43.495 


5.154 


-1.252 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 


298.15 


60.850 


47.152 


-34.563 


300 


60.850 


47.066 


-34.287 


400 


60.732 


42.483 


-23.211 


500 


60.466 


37.950 


-16.588 


600 


60.148 


33.476 


-12.193 


700 


59.787 


29.058 


-9.072 


800 


59.377 


24.695 


-6.746 


900 


58.918 


20.387 


-4.951 


964 


58.598 


17.659 


-4.003 


964 


58.083 


17.659 


-4.003 


1000 


57.894 


16.152 


-3.530 


1100 


57.336 


12.005 


-2.385 


1200 


56.732 


7.910 


-1.441 


1300 


56.086 


3.868 


- .650 


1400 


55.399 


- .125 


.020 



Phase change : 964 K, a-6 transition of CoSO^(c); 
AH° = 0.515 kcal/mol. 



TABLE 57. - Thermodynamic data for the reaction 
NiS0^(c) = NiO(c) + SOjCg) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 





56.234 


56.234 


00 


100 


56.752 


52.203 


-114.087 


200 


56.856 


47.594 


-52.008 


298.15 


56.830 


43.051 


-31.557 


300 


56.832 


42.966 


-31.301 


400 


56.712 


38.362 


-20.960 


500 


56.628 


33.775 


-14.763 


525 


56.661 


32.636 


-13.586 


525 


56.661 


32.636 


-13.586 


565 


56.597 


30.804 


-11.915 


565 


56.597 


30.804 


-11.915 


600 


56.498 


29.211 


-10.640 


700 


56.155 


24.686 


-7.707 


800 


55.757 


20.236 


-5.528 


900 


55.278 


15.809 


-3.839 


1000 


54.768 


11.457 


-2.504 


1100 


54.237 


7.162 


-1.423 


1200 


53.680 


2.888 


- .526 



Phase changes ; 525 K, a-3 transition point of 

NiO; AH° = kcal/mol. 

565 K, 8-6 transition point of 

NiO; Ah° = kcal/mol. 



TABLE 58. - Thermodynamic data for the reaction 
2CuS0^(c) = CuO•CuSO^(c) + SOjCg) 



T, K 


kcal 


AG% 
kcal 


Log K 





54.279 


54.279 


00 


100 


54.908 


50.027 


-109.333 


200 


55.023 


45.071 


-49.251 


298.15 


54.920 


40.204 


-29.470 


300 


54.916 


40.112 


-29.221 


400 


54.649 


35.215 


-19.240 


500 


54.276 


30.397 


-13.287 


600 


53.828 


25.663 


-9.348 


700 


53.308 


21.009 


-6.559 


800 


52.698 


16.437 


-4.490 


900 


51.983 


11.944 


-2.900 


1000 


51.174 


7.540 


-1.648 


11GG 


50.301 


3.215 


- .639 



TABLE 59.- Thermodynamic data for the reaction 
CuO»CuSO,»(c) = 2CuO(c) + SOjCg) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 





49.839 


49.839 


00 


100 


50.166 


46.006 


-100.545 


200 


50.143 


41.856 


-45.738 


298.15 


50.120 


37.787 


-27.698 


300 


50.118 


37.711 


-27.472 


400 


49.965 


33.595 


-18.355 


500 


49.726 


29.529 


-12.907 


600 


49.426 


25.516 


-9.294 


700 


49.098 


21.557 


-6.730 


800 


48.752 


17.646 


-4.821 


900 


48.381 


13.781 


-3.347 


1000 


47.960 


9.958 


-2.176 


1100 


47.461 


6.179 


-1.228 


1200 


46.855 


2.455 


- .447 



41 



TABLE 60. - Thermodynamic data for the reaction 
3ZnS0,»(c) = ZnO*2ZnSO^(c) + SOjCg) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 


298.15 


57.890 


42.910 


-31.453 


300 


57.885 


42.816 


-31.191 


400 


57.787 


37.812 


-20.659 


500 


57.674 


32.830 


-14.350 


600 


57.325 


27.887 


-10.158 


700 


56.642 


23.032 


-7.191 


800 


55.558 


18.300 


-4.999 


900 


54.037 


13.727 


-3.333 


1000 


52.059 


9.350 


-2.043 


1015 


51.177 


8.168 


-1.759 


1015 


36.567 


8.168 


-1.759 


1100 


36.418 


5.797 


-1.152 


1200 


36.411 


3.014 


- .549 



Phase change ; 1015 K, a-3 transition point for 
ZnSO^Cc); AH'r 4.87 kcal/mol. 



TABLE 61. - Thermodynamic data for the reaction 
0.5ZnO*2ZnSOH(c) = 1.5ZnO(c) + SOjCg) 



T, K 


AH% 
kcal 


AG% 
kcal 


Log K 


298.15 


54.932 


42.143 


-30.891 


300 


54.928 


42.063 


-30.643 


400 


54.666 


37.811 


-20.659 


500 


54.300 


33.638 


-14.703 


600 


53.905 


29.548 


-10.763 


700 


53.495 


25.514 


-7.966 


800 


53.072 


21.544 


-5.885 


900 


52.633 


17.627 


-4.280 


1000 


52.173 


13.762 


-3.008 


1100 


51.688 


9.951 


-1.977 


1200 


51.175 


6.175 


-1.125 



42 



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43 

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45 



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